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CHAPTER 7 QUANTUM THEORY AND
ATOMIC STRUCTURE
The value for the speed of light will be 3.00x108 m/s except when more significant figures are necessary, in which cases,
2.9979x108 m/s will be used.

FOLLOW–UP PROBLEMS

7.1A Plan: Given the frequency of the light, use the equation c = λν to solve for wavelength.
Solution:
c 3.00x108 m/s  1 nm 
λ= =   = 414.938 = 415 nm
ν 7.23x1014 s −1  10−9 m 
c 3.00x108 m/s  1 Å 
λ= =   = 4149.38 = 4150 Å
ν 7.23x1014 s −1  10−10 m 

7.1B Plan: Given the wavelength of the light, use the equation c = λν to solve for frequency. Remember that
wavelength must be in units of m in this equation.
Solution:
c 3.00x108 m/s 109 nm
ν= =� �� � = 3.1915x1014 = 3.2x1014 s–1
λ 940 nm 1m
This is infrared radiation.

7.2A Plan: Use the formula E = hν to solve for the frequency. Then use the equation c = λν to solve for the wavelength.
Solution:
–19
E 8.2x10 J
ν= =� –34
� = 1.2375x1015 = 1.2x1015 s–1
h 6.626x10 J•s
(using the unrounded number in the next calculation to avoid rounding errors)

c 3.00x108 m/s 109 nm

λ= =� � � � = 240 nm
ν 1.2375x1015 s–1 1m

7.2B Plan: To calculate the energy for each wavelength we use the formula E = hc/λ.
Solution:

E=
hc
=
(
6.626x10−34 J • s)(3.00x108 m/s )
= 1.9878x10–17 = 2x10–17 J
λ 1x10−8 m

E=
hc
=
(
6.626x10−34 J • s)(3.00x108 m/s )
= 3.9756x10–19 = 4x10–19 J
λ 5x10−7 m

E=
hc
=
(
6.626x10−34 J • s)(3.00x108 m/s )
= 1.9878x10–21 = 2x10–21 J
λ 1x10 m−4

As the wavelength of light increases from ultraviolet to visible to infrared, the energy of the light decreases.

7-1
  1 1 
7.3A Plan: Use the equation relating ΔE = – 2.18x10– 18 J  2 − 2  to find the energy change; a photon in
n n initial 
 final
the IR (infrared) region is emitted when has n has a final value of 3. Then use E = hc/λ to find the wavelength of
the photon.
Solution:
 1 1 
a) ΔE = – 2.18x10– 18 J  2 − 2 
n n initial 
 final
 1 1 
ΔE = – 2.18x10– 18 J  2 − 2 
3 6 
ΔE = –1.8166667x10– 19 = –1.82x10– 19 J

hc
b) E =
λ

λ =
hc
=
(
6.626x10−34 J • s 3.00x108 m/s  1 Å )( )
 −10  = 1.094202x10 = 1.09x10 Å
4 4
−19
E 1.8166667x10 J  10 m 

7.3B Plan: Use the equation E = hc/λ to find the energy change for this reaction. Then use the equation
 1 1 
ΔE = – 2.18x10– 18 J  2 − 2  to find the final energy level to which the electron moved.
n n initial 
 final
Solution:
(6.626x10–34 J•s) (3.00x108 m/s) 109 nm
a) ΔE = hc/λ = � �� � = ΔE = 4.8483x10–19 = 4.85x10–19 J
410. nm 1m
Because the photon is emitted, energy is being given off, so the sign of ΔE should be negative. Therefore,
ΔE = –4.85x10–19 J
–4.85x10–19 J 6.022x1023 H atoms 1 kJ
ΔE (kJ/mol) = � �� �� � = –292 kJ/mol (number of atoms is a positive
1 H atom 1 mol H 1000 J
number)
 1 1 
b) ΔE = – 2.18x10– 18 J  2 − 2 
n
 final n initial 
1 ΔE 1
= +
n2final –2.18x10 –18
J n2initial
–19
1 –4.85x10 J 1
= +
n2final –2.18x10
–18
J 62
1
= 0.25025
n2final
n2final = 3.9960 = 4 (The final energy level is an integer, so its square is also an integer.)
n final = 2

7.4A Plan: With the equation for the de Broglie wavelength, λ = h/mu and the given de Broglie wavelength, calculate
the electron speed. The wavelength must be expressed in meters. Use the same formulas to calculate the speed of
the golf ball. The mass of both the electron and the golf ball must be expressed in kg in their respective
calculations.

7-2
 Solution:
a) λ = h/mu
h 6.626 x10−34 J • s  kg • m 2 /s 2 
u= =   = 7273.3 = 7.27x103 m/s
  10−9 m   
( )
mλ J 
9.11x10 kg (100.nm ) 
−31
 
  1 nm  
1 kg
b) Mass (kg) of the golf ball = (45.9 g) � � = 0.0459 kg
1000 g
h 6.626x10–34 J•s kg•m2 /s2
u= = –9
� � = 1.4436x10–25 = 1.44x10–25 m/s
mλ (0.0459 10 J
kg)�(100. nm)� ��
1 nm

7.4B Plan: Use the equation for the de Broglie wavelength, λ = h/mu with the given mass and speed to calculate the de
Broglie wavelength of the racquetball. The mass of the racquetball must be expressed in kg, and the speed must be
expressed in m/s in the equation for the de Broglie wavelength.
Solution:
1 kg
Mass (kg) of the racquetball = (39.7 g) � � = 0.0397 kg
1000 g
55 mi 1 hr 1.609 km 1000 m
Speed (m/s) of the racquetball = � �� �� �� � = 24.5819 = 25 m/s
hr 3600 s mi 1 km
λ = h/mu
h 6.626x10–34 J•s
λ= = = 6.67607x10–34 = 6.7x10–34 m
mu (0.0397 kg)(25 m/s)

h
7.5A Plan: Use the equation ∆x • m∆u ≥ to solve for the uncertainty (Δx) in position of the baseball.
4π
Solution:
h
∆x • m∆u ≥
4π
Δu = 1% of u = 0.0100(44.7 m/s) = 0.447 m/s
h 6.626x10−34 J • s
∆x ≥ = = 8.3070285x10– 34
4πm∆u 4π ( 0.142 kg )( 0.447 m/s )
Δx ≥ 8.31x10– 34 m

h
7.5B Plan: Use the equation ∆x • m∆u ≥ to solve for the uncertainty (Δx) in position of the neutron.
4π
Solution:
h
∆x • m∆u ≥
4π
Δu = 1% of u = 0.0100(8x107 m/s) = 8x105 m/s
h 6.626x10–34 J•s
∆x ≥ = = 3.9467x10– 14 m
4πm∆u 4π�1.67x10–27 kg�(8x105 m/s)
Δx ≥ 4x10– 14 m

7.6A Plan: Following the rules for l (integer from 0 to n – 1) and m l (integer from –l to +l), write quantum numbers for
n = 4.
Solution:
For n = 4 l = 0, 1, 2, 3
For l = 0, m l = 0

7-3
 For l = 1, m l = –1, 0, 1
For l = 2, m l = –2, –1, 0, 1, 2
For l = 3, m l = –3, –2, –1, 0, 1, 2, 3

7.6B Plan: Following the rules for l (integer from 0 to n – 1) and m l (integer from –l to +l), determine which value of
the principal quantum number has five allowed levels of l.
Solution:
The number of possible l values is equal to n, so the n = 5 principal quantum number has five allowed values of l.
For n = 5 l = 0, 1, 2, 3, 4
For l = 0, m l = 0
For l = 1, m l = –1, 0, 1
For l = 2, m l = –2, –1, 0, 1, 2
For l = 3, m l = –3, –2, –1, 0, 1, 2, 3
For l = 4, m l = –4, –3, –2, –1, 0, 1, 2, 3, 4

7.7A Plan: Identify n and l from the sublevel designation. n is the integer in front of the sublevel letter. The sublevels
are given a letter designation, in which s represents l = 0, p represents l = 1, d represents l = 2, f represents l = 3.
Knowing the value for l, find the m l values (integer from –l to +l).
Solution:
Sublevel name n value l value m l values
2p 2 1 –1, 0, 1
5f 5 3 –3, –2, –1, 0, 1, 2, 3

7.7B Plan: Identify n and l from the sublevel designation. n is the integer in front of the sublevel letter. The sublevels
are given a letter designation, in which s represents l = 0, p represents l = 1, d represents l = 2, f represents l = 3.
Knowing the value for l, find the m l values (integer from –l to +l).
Solution:
Sublevel name n value l value m l values
4d 4 2 –2, –1, 0, 1, 2
6s 6 0 0
The number of orbitals for each sublevel equals 2l + 1. Sublevel 4d should have 5 orbitals and sublevel 6s should
have 1 orbital. Both of these agree with the number of m l values for the sublevel.

7.8A Plan: Use the rules for designating quantum numbers to fill in the blanks.
For a given n, l can be any integer from 0 to n–1.
For a given l, m l can be any integer from – l to + l.
The sublevels are given a letter designation, in which s represents l = 0, p represents l = 1, d represents l = 2,
f represents l = 3.
Solution:
The completed table is:
n l ml Name
a) 4 1 0 4p
b) 2 1 0 2p
c) 3 2 –2 3d
d) 2 0 0 2s

7.8B Plan: Use the rules for designating quantum numbers to determine what is wrong with the quantum number
designations provided in the problem.
For a given n, l can be any integer from 0 to n–1.
For a given l, m l can be any integer from – l to + l.
The sublevels are given a letter designation, in which s represents l = 0, p represents l = 1, d represents l = 2,
f represents l = 3.

7-4
 Solution:
The provided table is:
n l ml Name
a) 5 3 4 5f
b) 2 2 1 2d
c) 6 1 –1 6s
a) For l = 3, the allowed values for m l are –3, –2, –1, 0, 1, 2, 3, not 4
b) For n = 2, l = 0 or 1 only, not 2; the sublevel is 2p, since m l = 1.
c) The value l = 1 indicates the p sublevel, not the s; the sublevel name is 6p.

TOOLS OF THE LABORATORY BOXED READING PROBLEMS

B7.1 Plan: Plot absorbance on the y-axis and concentration on the x-axis. Since this is a linear plot, the graph is of the
type y = mx + b, with m = slope and b = intercept. Any two points may be used to find the slope, and the slope is
used to find the intercept. Once the equation for the line is known, the absorbance of the solution in part b) is
used to find the concentration of the diluted solution, after which the dilution equation is used to find the
molarity of the original solution.
Solution:
a) Absorbance vs. Concentration:

0.45
0.4
Absorbance

0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0 0.00001 0.00002 0.00003 0.00004

Concentration (M)

This is a linear plot, thus, using the first and last points given:
y − y1 ( 0.396 − 0.131)
m= 2 = 13,250 = 1.3x104/M
( )
= − −
x2 − x1 3.0x10 − 1.0x10 M
5 5

Using the slope just calculated and any of the data points, the value of the intercept may be found.
b = y – mx = 0.396 – (13,250/M)(3.0x10–5 M) = –0.0015 = 0.00 (absorbance has no units)
b) Use the equation just determined: y = (1.3x104/M) x + 0.00.
x = (y – 0.00)/(1.3x104/M) = (0.236/1.3x104) M = 1.81538x10–5 M = 1.8x10–5 M
This value is M f in a dilution problem (M i V i )= (M f V f ) with V i = 20.0 mL and V f = 150. mL.

Mi =
(M f )(Vf )
=
(1.81538x10 −5
)
M (150. mL )
= 1.361538x10–4 = 1.4x10–4 M
(Vi ) ( 20.0 mL )
B7.2 Plan: The color of light associated with each wavelength can be found from Figure 7.3. The
c
frequency of each wavelength can be determined from the relationship c = λν or ν = . The
λ

7-5
 wavelength in nm must be converted to meters.
Solution:
3.00x108 m/s  1 nm 
a) red ν= 
14 14 –1
 = 4.4709x10 = 4.47x10 s
671 nm  10−9 m 
3.00x108 m/s  1 nm 
b) blue ν= 14
 −9  = 6.6225x10 = 6.62x10 s
14 –1
453 nm  10 m 
3.00x108 m/s  1 nm 
c) yellow-orange ν = 
14 14 –1
 = 5.0933786x10 = 5.09x10 s
589 nm  10−9 m 

END–OF–CHAPTER PROBLEMS

7.1 All types of electromagnetic radiation travel as waves at the same speed. They differ in both their frequency,
wavelength, and energy.

7.2 Plan: Recall that the shorter the wavelength, the higher the frequency and the greater the energy. Figure 7.3
describes the electromagnetic spectrum by wavelength and frequency.
Solution:
a) Wavelength increases from left (10–2 nm) to right (1012 nm) in Figure 7.3. The trend in increasing wavelength
is: x-ray < ultraviolet < visible < infrared < microwave < radio wave.
b) Frequency is inversely proportional to wavelength according to the equation c = λν, so frequency has the
opposite trend: radio wave < microwave < infrared < visible < ultraviolet < x-ray.
c) Energy is directly proportional to frequency according to the equation E = hν. Therefore, the trend in increasing
energy matches the trend in increasing frequency: radio wave < microwave < infrared < visible < ultraviolet <
x-ray.

7.3 a) Refraction is the bending of light waves at the boundary of two media, as when light travels from air into water.
b) Diffraction is the bending of light waves around an object, as when a wave passes through a slit about as wide as
its wavelength.
c) Dispersion is the separation of light into its component colors (wavelengths), as when light passes through a
prism.
d) Interference is the bending of light through a series of parallel slits to produce a diffraction pattern of
brighter and darker spots.
Note: Refraction leads to a dispersion effect and diffraction leads to an interference effect.

7.4 Evidence for the wave model is seen in the phenomena of diffraction and refraction. Evidence for the particle model
includes the photoelectric effect and blackbody radiation.

7.5 a) Frequency: C < B < A

b) Energy: C < B < A
c) Amplitude: B < C < A
d) Since wave A has a higher energy and frequency than B, wave A is more likely to cause a current.
e) Wave C is more likely to be infrared radiation since wave C has a longer wavelength than B.

7.6 Radiation (light energy) occurs as quanta of electromagnetic radiation, where each packet of energy is called a
photon. The energy associated with this photon is fixed by its frequency, E = hν. Since energy depends on frequency,
a threshold (minimum) frequency is to be expected. A current will flow as soon as a photon of sufficient energy
reaches the metal plate, so there is no time lag.

7.7 Plan: Wavelength is related to frequency through the equation c = λν. Recall that a Hz is a reciprocal second, or
1/s = s–1. Assume that the number “950” has three significant figures.

7-6
 Solution:
c = λν
c 3.00x108 m/s
λ (m) = = = 315.789 = 316 m
ν  103 Hz   s −1 
( 950. kHz )    
 1 kHz   Hz 
 1 nm 
= ( 315.789 m )  −9
c
λ (nm) = 11 11
 = 3.15789x10 = 3.16x10 nm
ν  10 m 
 1Å 
= ( 315.789 m )  −10  = 3.158x1012 = 3.16x1012 Å
c
λ (Å) =
ν  10 m 

7.8 Wavelength and frequency relate through the equation c = λν. Recall that a Hz is a reciprocal second, or 1/s = s–1.
c 3.00x108 m/s
λ (m) = = = 3.208556 = 3.21 m
ν  106 Hz   s −1 
( 93.5 MHz )    
 1 MHz   Hz 
 1 nm 
= ( 3.208556 m )  −9
c
λ (nm) = 9 9
 = 3.208556x10 = 3.21x10 nm
ν  10 m 
 1Å 
= ( 3.208556 m )  −10  = 3.208556x1010 = 3.21x1010 Å
c
λ (Å) =
ν  10 m 

7.9 Plan: Frequency is related to energy through the equation E = hν. Note that 1 Hz = 1 s–1.
Solution:
E = hν
E = (6.626x10–34 J•s)(3.8x1010 s–1) = 2.51788x10–23 = 2.5x10–23 J

hc (6.626x10 −34
)( )
J•s 3.00x108 m/s  1 Å 
–15 –15
7.10 E= =  −10  = 1.5291x10 = 1.5x10 J
λ 1.3 Å  10 m 

hc
7.11 Plan: Energy is inversely proportional to wavelength ( E = ). As wavelength decreases, energy increases.
λ
Solution:
In terms of increasing energy the order is red < yellow < blue.

7.12 Since energy is directly proportional to frequency (E = hν): UV (ν = 8.0x1015 s–1) > IR (ν = 6.5x1013 s–1) >
microwave (ν = 9.8x1011 s–1) or UV > IR > microwave.

7.13 Plan: Wavelength is related to frequency through the equation c = λν. Recall that a Hz is a reciprocal second,
or 1/s = s–1.
Solution:
 109 Hz   s −1 
ν = (s–1) = ( 22.235 GHz )  = 2.2235x1010 s–1
 1 GHz   Hz 
  
c 2.9979x108 m/s  1 nm 
λ (nm) = = 
7 7
 = 1.3482797x10 = 1.3483x10 nm
ν 2.2235x1010 s −1  10−9 m 
c 2.9979x108 m/s  1 Å 
λ (Å) = = 
8 8
 = 1.3482797x10 = 1.3483x10 Å
ν 2.2235x1010 s −1  10−10 m 

7-7
7.14 Frequency and wavelength can be calculated using the speed of light: c = λν.
c 3.00x108 m/s  1 µm 
a) ν = = 13
 −6  = 3.125x10 = 3.1x10 s
13 –1
λ 9.6 µm  10 m 
c 2.9979x108 m/s  1 µm 
b) λ (µm) = =   = 3.464979 = 3.465 µm
ν  s   10−6 m 
−
( )
1
13
8.652x10 Hz  
 Hz 

7.15 Frequency and energy are related by E = hν, and wavelength and energy are related by E = hc/λ.
 106 eV   1.602x10−19 J 
(1.33 MeV )     Hz
ν (Hz) =
E  1 MeV   1 eV   20 20
=  −1  = 3.2156x10 = 3.22x10 Hz
h 6.626x10−34 J•s s 

λ (m) =
hc
=
( 6.626x10 −34
)(
J•s 3.00x108 m/s )
= 9.32950x10–13 = 9.33x10–13 m
E  10 eV   1.602x10 J 
6 −19
(1.33 MeV )    
 1 MeV   1 eV 
The wavelength can also be found using the frequency calculated in the equation c = λν.

7.16 Plan: The least energetic photon in part a) has the longest wavelength (242 nm). The most energetic photon in
part b) has the shortest wavelength (2200 Å). Use the relationship c = λν to find the frequency of the photons and
hc
relationship E = to find the energy.
λ
Solution:
a) c = λν
c 3.00x108 m/s  1 nm 
ν= = 
15 15 –1
 = 1.239669x10 = 1.24x10 s
λ 242 nm  10−9 m 

hc ( 6.626x10 −34
)(
J•s 3.00x108 m/s  1 nm  )–19 –19
E= =  −9  = 8.2140x10 = 8.21x10 J
λ 242 nm  10 m 
c 3.00x10 m/s  1 Å 
8
b) ν = = 
15 15 –1
 = 1.3636x10 = 1.4x10 s
λ 2200 Å  10−10 m 

hc (6.626x10 −34
)( )
J•s 3.00x108 m/s  1 Å 
–19 –19
E= =  −10  = 9.03545x10 = 9.0x10 J
λ 2200 Å  10 m 

7.17 “n” in the Rydberg equation is equal to a Bohr orbit of quantum number “n” where n = 1, 2, 3, ...∞.

7.18 Bohr’s key assumption was that the electron in an atom does not radiate energy while in a stationary state, and the
electron can move to a different orbit by absorbing or emitting a photon whose energy is equal to the difference in
energy between two states. These differences in energy correspond to the wavelengths in the known spectra for
the hydrogen atoms. A Solar System model does not allow for the movement of electrons between levels.

7.19 An absorption spectrum is produced when atoms absorb certain wavelengths of incoming light as electrons move
from lower to higher energy levels and results in dark lines against a bright background. An emission spectrum is
produced when atoms that have been excited to higher energy emit photons as their electrons return to lower
energy levels and results in colored lines against a dark background. Bohr worked with emission spectra.

7.20 Plan: The quantum number n is related to the energy level of the electron. An electron absorbs energy to
change from lower energy (lower n) to higher energy (higher n), giving an absorption spectrum. An electron emits
energy as it drops from a higher energy level (higher n) to a lower one (lower n), giving an emission spectrum.

7-8
 Solution:
a) The electron is moving from a lower value of n (2) to a higher value of n (4): absorption
b) The electron is moving from a higher value of n (3) to a lower value of n (1): emission
c) The electron is moving from a higher value of n (5) to a lower value of n (2):emission
d) The electron is moving from a lower value of n (3) to a higher value of n (4): absorption

7.21 The Bohr model works only for a one-electron system. The additional attractions and repulsions in many-electron
systems make it impossible to predict accurately the spectral lines.

7.22 The Bohr model has successfully predicted the line spectra for the H atom and Be3+ ion since both are one-

electron species. The energies could be predicted from E n =

( )( 2.18x10 J )
− Z2 −18

where Z is the atomic number

n2
for the atom or ion. The line spectra for H would not match the line spectra for Be3+ since the H nucleus contains
one proton while the Be3+ nucleus contains 4 protons (the Z values in the equation do not match); the force of
attraction of the nucleus for the electron would be greater in the beryllium ion than in the hydrogen atom. This
means that the pattern of lines would be similar, but at different wavelengths.

7.23 Plan: Calculate wavelength by substituting the given values into Equation 7.3, where n 1 = 2 and n 2 = 5 because
n 2 > n 1 . Although more significant figures could be used, five significant figures are adequate for this calculation.
Solution:
1  1 1 
= R 2 − 2  R = 1.096776x107 m–1
λ  
 1
n n2 
n1 = 2 n2 = 5
 1 1 
1
( )
 1 1 
= R  2 − 2  = 1.096776x107 m −1  2 − 2  = 2,303,229.6 m–1
λ n   
 1 n2  2 5
 1   1 nm 
λ (nm) =  −1   −9  = 434.1729544 = 434.17 nm
 2,303, 229.6 m   10 m 

7.24 Calculate wavelength by substituting the given values into the Rydberg equation, where n 1 = 1 and n 2 = 3 because
n 2 > n 1 . Although more significant figures could be used, five significant figures are adequate for this calculation.
 1 1 
1
( )
1 1 
= R  2 − 2  = 1.096776x107 m −1  2 − 2  = 9,749,120 m–1
λ   1 3 
 n1 n2 
 1   1Å 
λ (Å) =  −1   −10  = 1025.7336 = 1025.7 Å
 9,749,120 m   10 m 

7.25 Plan: The Rydberg equation is needed. For the infrared series of the H atom, n 1 equals 3. The least energetic
spectral line in this series would represent an electron moving from the next highest energy level, n 2 = 4.
Although more significant figures could be used, five significant figures are adequate for this calculation.
Solution:
 1 1 
1
( )
 1
= R  2 − 2  = 1.096776x107 m −1  2 − 2  = 533,155 m–1
λ n  3
1 
4 
 1 n2 
 1   1 nm 
λ (nm) =  −1   −9  = 1875.627 = 1875.6 nm
 533,155 m   10 m 

7.26 Plan: The Rydberg equation is needed. For the visible series of the H atom, n 1 equals 2. The least energetic
spectral line in this series would represent an electron moving from the next highest energy level, n = 3. Although
more significant figures could be used, five significant figures are adequate for this calculation.

7-9
 Solution:
 1 1 
1
(  1 1 
)
= R  2 − 2  = 1.096776x107 m −1  2 − 2  = 1,523,300 m–1
λ n   
 1 n2  2 3
 1   1 nm 
λ (nm) =  −1   −9  = 656.4695 = 656.47 nm
 1,523,300 m   10 m 

7.27 Plan: To find the transition energy, use the equation for the energy of an electron transition and multiply by
Avogadro’s number to convert to energy per mole.
Solution:
 1 1 
( )
∆E = −2.18x10−18 J  2
n
− 2 
ninitial 
 final

( )  1
2
1 
∆E = −2.18x10−18 J  2 − 2  = –4.578x10–19 J/photon
5 
 −4.578x10 − 19
J   6.022x1023 photons 
∆E =   
5 5
 = –2.75687x10 = –2.76x10 J/mol
 photon 1 mol 
  
The energy has a negative value since this electron transition to a lower n value is an emission of energy.

7.28 To find the transition energy, use the equation for the energy of an electron transition and multiply by Avogadro’s
number.
 1 1 
( )
∆E = −2.18x10−18 J  2
n
− 2 
ninitial 
 final

( )  1
3
1
∆E = −2.18x10−18 J  2 − 2  = 1.93778x10–18 J/photon
1 
 1.93778x10 − 18
J   6.022x1023 photons 
∆E =   
6 6
 = 1.1669x10 = 1.17x10 J/mol
 photon 1 mol
  

7.29 Plan: Determine the relative energy of the electron transitions. Remember that energy is directly proportional
to frequency (E = hν).
Solution:
Looking at an energy chart will help answer this question.
n=5 n=4

(d) n=3

(a) (c)
n=2

(b)

n=1

Frequency is proportional to energy so the smallest frequency will be d) n = 4 to n = 3; levels 3 and 4 have a
smaller ∆E than the levels in the other transitions. The largest frequency is b) n = 2 to n = 1 since levels 1 and
2 have a larger ∆E than the levels in the other transitions. Transition a) n = 2 to n = 4 will be smaller than
transition c) n = 2 to n = 5 since level 5 is a higher energy than level 4. In order of increasing frequency the
transitions are d < a < c < b.
7.30 b>c>a>d

7-10
7.31 Plan: Use the Rydberg equation. Since the electron is in the ground state (lowest energy level), n 1 = 1. Convert
the wavelength from nm to units of meters.
Solution:
 10−9 m 
λ = ( 97.20 nm )  = 9.720x10–8 m
 1 nm 
ground state: n 1 = 1; n 2 = ?
 
 
1
λ
(
= 1.096776x107 m −1 )  n1 2
−
1
n22

 1 
1 1 
1
−8 (
= 1.096776x107 m −1  2 − 2 
 n2 
)
9.72x10 m 1
1 1 
0.93803 =  2 − 2 
1 n2 

1
= 1 – 0.93803 = 0.06197
n22
n22 = 16.14
n2 = 4

 10−9 m 
7.32 λ = (1281 nm )  –6
 = 1.281x10 m
 1 nm
 
 1 1 
1
λ
(
= 1.096776x107 m −1  2 − 2 
 n2 
)
 n1
 
1
1.281x10−6 m
(
= 1.096776x107 m −1 )  n1
2
−
1
52

 1 
 1 1 
0.07118 =  2 − 2 
n 5 
 1
1
= 0.07118 + 0.04000 = 0.11118
n12
n12 = 8.9944
n1 = 3

hc ( 6.626x10 −34
)(
J•s 3.00x108 m/s  1 nm  )–19 –19
7.33 E= =  −9  = 4.55917x10 = 4.56x10 J
λ ( 436 nm )  10 m 

7.34 a) Absorptions: A, C, D; Emissions: B, E, F

b) Energy of emissions: E < F < B
c) Wavelength of absorption: D < A < C

7.35 If an electron occupies a circular orbit, only integral numbers of wavelengths (= 2nπr) are allowed for acceptable
standing waves. A wave with a fractional number of wavelengths is forbidden due to destructive interference with
itself. In a musical analogy to electron waves, the only acceptable guitar string wavelengths are those that are an
integral multiple of twice the guitar string length (2 L).

7.36 De Broglie’s concept is supported by the diffraction properties of electrons demonstrated in an electron
microscope.

7-11
7.37 Macroscopic objects have significant mass. A large m in the denominator of λ = h/mu will result in a very small
wavelength. Macroscopic objects do exhibit a wavelike motion, but the wavelength is too small for humans to see
it.

7.38 The Heisenberg uncertainty principle states that there is fundamental limit to the accuracy of measurements. This
limit is not dependent on the precision of the measuring instruments, but is inherent in nature.

7.39 Plan: Use the de Broglie equation. Mass in lb must be converted to kg and velocity in mi/h must
be converted to m/s because a joule is equivalent to kg•m2/s2.
Solution:
 1 kg 
a) Mass (kg) = ( 232 lb )   = 105.2154 kg
 2.205 lb 
 19.8 mi   1 km   10 m   1 h 
3
Velocity (m/s) =        = 8.87097 m/s
 h   0.62 mi   1 km   3600 s 

λ=
h ( 6.626x10 −34
J•s

)
 kg•m 2 /s2  –37 –37
=
 m    = 7.099063x10 = 7.10x10 m
mu
(105.2154 kg )  8.87097  J 
 s 
 0.1 mi   1 km   10 m   1 h 
3
b) Uncertainty in velocity (m/s) =        = 0.0448029 m/s
 h   0.62 mi   1 km   3600 s 
h
∆x•m∆v ≥
4π

∆x ≥
h
≥
( 6.626x10 −34


)
 kg•m 2 /s2 
J•s
 ≥ 1.11855x10 ≥ 1x10 m
–35 –35
4 π m∆v  0.0448029 m  
4π (105.2154 kg ) 
J 

 s 

a) λ =
h ( 6.626x10 J•s )  kg•m /s
−34 2 2   103 g   0.62 mi   1 km   3600 s 
   
7.40 =
  3  
mu
( 6.6x10 g )  3.4x10 mih   J
−24 7   1 kg   1 km   10 m   1 h 

= 6.59057x10–15 = 6.6x10–15 m
h
b) ∆x•m∆v ≥
4π

∆x ≥
h
≥
(6.626x10 J•s )
−34
 kg•m 2 /s2   103 g   0.62 mi   1 km   3600 s 

4 π m∆v mi  
 0.1x10   1 kg   1 km   103 m   1 h 
4π ( 6.6x10 g ) 
7
−24 J     

 h 
≥ 1.783166x10 ≥ 2x10 m
–14 –14

7.41 Plan: Use the de Broglie equation. Mass in g must be converted to kg and wavelength in Ǻ must be converted to
m because a joule is equivalent to kg•m2/s2.
Solution:
 1 kg 
Mass (kg) = ( 56.5 g )  3  = 0.0565 kg
 10 g 
 
 10−10 m 
Wavelength (m) = ( 5400 Å )  = 5.4x10–7 m
 1 Å 
 

7-12
 h
λ=
mu

u=
h
=
(
6.626x10−34 J•s  kg•m 2 /s2 

) –26 –26
 = 2.1717x10 = 2.2x10 m/s
mλ (
( 0.0565 kg ) 5.4x10 m 
− 7  J 
 )
h
7.42 λ=
mu

h ( 
)
6.626x10−34 J•s  kg•m 2 /s2   103 g   1 pm 
  = 4.666197x10–23 = 4.67x10–23 m/s
(142 g )(100. pm )  J   1 kg   10−12 m 
u= =
mλ

7.43 Plan: The de Broglie wavelength equation will give the mass equivalent of a photon with known wavelength and
velocity. The term “mass equivalent” is used instead of “mass of photon” because photons are quanta of
electromagnetic energy that have no mass. A light photon’s velocity is the speed of light, 3.00x108 m/s.
Wavelength in nm must be converted to m.
Solution:
 10−9 m 
Wavelength (m) = ( 589 nm )  = 5.89x10–7 m
 1 nm 
 
h
λ=
mu

m=
h
=
(
6.626x10 J•s −34
)  kg•m 2 /s2

 –36 –36
 = 3.7499x10 = 3.75x10 kg/photon
λu ( )(
5.89x10−7 m 3.00 x108 m/s )  J 

h
7.44 λ=
mu

m=
h
=
(
6.626x10 J•s −34
)  kg•m 2 /s2

  1 nm  –36
  −9  = 3.2916x10 kg/photon
λu (
( 671 nm ) 3.00x108 m/s )  J  10 m 
 3.2916x10−36 kg   6.022x1023 photons  –12 –12
    = 1.9822x10 = 1.98x10 kg/mol
 photon  mol 

7.45 The quantity ψ2 expresses the probability of finding an electron within a specified tiny region of space.

7.46 Since ψ2 is the probability of finding an electron within a small region or volume, electron density would
represent a probability per unit volume and would more accurately be called electron probability density.

7.47 A peak in the radial probability distribution at a certain distance means that the total probability of finding the
electron is greatest within a thin spherical volume having a radius very close to that distance. Since principal
quantum number (n) correlates with distance from the nucleus, the peak for n = 2 would occur at a greater
distance from the nucleus than 0.529 Å. Thus, the probability of finding an electron at 0.529 Å is much greater for
the 1s orbital than for the 2s.

7.48 a) Principal quantum number, n, relates to the size of the orbital. More specifically, it relates to the distance from
the nucleus at which the probability of finding an electron is greatest. This distance is determined by the energy of
the electron.
b) Angular momentum quantum number, l, relates to the shape of the orbital. It is also called the azimuthal
quantum number.

7-13
 c) Magnetic quantum number, m l , relates to the orientation of the orbital in space in three-dimensional space.

7.49 Plan: The following letter designations correlate with the following l quantum numbers:
l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed m l values are – l to +
l.
The number of orbitals of a particular type is given by the number of possible m l values.
Solution:
a) There is only a single s orbital in any shell. l = 1 and m l = 0: one value of m l = one s orbital.
b) There are five d orbitals in any shell. l = 2 and m l = –2, –1, 0, +1, +2. Five values of m l = five d orbitals.
c) There are three p orbitals in any shell. l = 1 and m l = –1, 0, +1. Three values of m l = three p orbitals.
d) If n = 3, l = 0(s), 1(p), and 2(d). There is a 3s (1 orbital), a 3p set (3 orbitals), and a 3d set (5 orbitals) for a
total of nine orbitals (1 + 3 + 5 = 9).

7.50 a) All f orbitals consist of sets of seven (l = 3 and m l = –3, –2, –1, 0, +1, +2, +3).
b) All p orbitals consist of sets of three (l = 1 and m l = –1, 0, +1).
c) All d orbitals consist of sets of five (l = 2 and m l = –2, –1, 0, +1, +2).
d) If n = 2, then there is a 2s (1 orbital) and a 2p set (3 orbitals) for a total of four orbitals (1 + 3 = 4).

7.51 Plan: Magnetic quantum numbers (m l ) can have integer values from –l to + l. The l quantum number can
have integer values from 0 to n – 1.
Solution:
a) l = 2 so m l = –2, –1, 0, +1, +2
b) n = 1 so l = 1 – 1 = 0 and m l = 0
c) l = 3 so m l = –3, –2, –1, 0, +1, +2, +3

7.52 Magnetic quantum numbers can have integer values from –l to +l. The l quantum number can
have integer values from 0 to n – 1.
a) l = 3 so m l = –3, –2, –1, 0, +1, +2, +3
b) n = 2 so l = 0 or 1; for l = 0, m l = 0; for l = l, m l = –1,0,+1
c) l = 1 so m l = –1, 0, +1

7.53 Plan: The s orbital is spherical; p orbitals have two lobes; the subscript x indicates that this orbital lies along
the x-axis.
Solution:
a) s: spherical b) p x : 2 lobes along the x-axis

z
z

x x

y y
The variations in coloring of the p orbital are a consequence of the quantum mechanical derivation of atomic
orbitals that are beyond the scope of this course.

7.54 a) p z : 2 lobes along the z-axis b) d xy : 4 lobes

7-14
 z
y

y x x

The variations in coloring of the p and d orbitals are a consequence of the quantum mechanical derivation of
atomic orbitals that are beyond the scope of this course.

7.55 Plan: The following letter designations for the various sublevels (orbitals) correlate with the following l quantum
numbers: l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed m l values
are – l to + l. The number of orbitals of a particular type is given by the number of possible m l values.
Solution:
sublevel allowable m l # of possible orbitals
a) d (l = 2) –2, –1, 0, +1, +2 5
b) p (l = 1) –1, 0, +1 3
c) f (l = 3) –3, –2, –1, 0, +1, +2, +3 7

7.56 sublevel allowable m l # of possible orbitals

a) s (l = 0) 0 1
b) d (l = 2) –2, –1, 0, +1, +2 5
c) p (l = 1) –1, 0, +1 3

7.57 Plan: The integer in front of the letter represents the n value. The letter designates the l value:
l = 0 = s orbital; l = 1 = p orbital; l = 2 = d orbital; l = 3 = f orbital. Remember that allowed m l values are – l to +
l.
Solution:
a) For the 5s subshell, n = 5 and l = 0. Since m l = 0, there is one orbital.
b) For the 3p subshell, n = 3 and l = 1. Since m l = –1, 0, +1, there are three orbitals.
c) For the 4f subshell, n = 4 and l = 3. Since m l = –3, –2, –1, 0, +1, +2, +3, there are seven orbitals.

7.58 a) n = 6; l = 4; 9 orbitals (m l = –4, –3, –2, –1, 0, +1, +2, +3, +4)
b) n = 4; l = 0; 1 orbital (m l = 0)
c) n = 3; l = 2; 5 orbitals (m l = –2, –1, 0, +1, +2)

7.59 Plan: Allowed values of quantum numbers: n = positive integers; l = integers from 0 to n – 1;
m l = integers from – l through 0 to + l.
Solution:
a) n = 2; l = 0; m l = –1: With n = 2, l can be 0 or 1; with l = 0, the only allowable m l value is 0. This
combination is not allowed. To correct, either change the l or m l value.
Correct: n = 2; l = 1; m l = –1 or n = 2; l = 0; m l = 0.
b) n = 4; l = 3; m l = –1: With n = 4, l can be 0, 1, 2, or 3; with l = 3, the allowable m l values are –3, –2, –1, 0, +1,
+2, +3. Combination is allowed.
c) n = 3; l = 1; m l = 0: With n = 3, l can be 0, 1, or 2; with l = 1, the allowable m l values are –1, 0, +1.
Combination is allowed.
d) n = 5; l = 2; m l = +3: With n = 5, l can be 0, 1, 2, 3, or 4; with l = 2, the allowable m l values are –2, –1, 0, +1,
+2. +3 is not an allowable m l value. To correct, either change l or m l value.
Correct: n = 5; l = 3; m l = +3 or n = 5; l = 2; m l = 0.

7-15
7.60 a) Combination is allowed.
b) No; n = 2; l = 1; m l = +1 or n = 2; l = 1; m l = 0
c) No; n = 7; l = 1; m l = +1 or n = 7; l = 3; m l = 0
d) No; n = 3; l = 1; m l = –1 or n = 3; l = 2; m l = –2

7.61 Determine the λ max for β-carotene by measuring its absorbance in the 610-640 nm region of the visible spectrum.
Prepare a series of solutions of β-carotene of accurately known concentration (using benzene or chloroform as
solvent), and measure the absorbance for each solution. Prepare a graph of absorbance versus concentration for these
solutions and determine its slope (assuming that this material obeys Beer’s law). Measure the absorbance of the
oil expressed from orange peel (diluting with solvent if necessary). The β-carotene concentration can then either
be read directly from the calibration curve or calculated from the slope (A = kC, where k = slope of the line and
C = concentration).

7.62 Plan: For Ppart a, use the values of the constants h, π, m e , and a 0 to find the overall constant in the equation.
hc
Use the resulting equation to calculate ∆E in part b). Use the relationship E = to calculate the wavelength in
λ
part c). Remember that a joule is equivalent to kg•m2/s2.

Solution:
a) h = 6.626x10–34 J•s; m e = 9.1094x10–31 kg; a 0 = 52.92x10–12 m
h2 h2  1 
E= − = −  2
8π 2
me a02 n 2 8π 2
me a02 n 

( 6.626x10 )
−34 2
J•s  kg•m 2 /s2  1 
E= −    2 
( )( )  n 
2
8π 2 9.1094x10−31 kg 52.92x10−12 m  J

 1   1 
= –(2.17963x10–18 J)  2  = –(2.180x10–18 J)  2 
n  n 
This is identical with the result from Bohr’s theory. For the H atom, Z = 1 and Bohr’s constant = –2.18x10–18 J.
For the hydrogen atom, derivation using classical principles or quantum-mechanical principles yields the same
constant.
b) The n = 3 energy level is higher in energy than the n = 2 level. Because the zero point of the atom’s energy is
defined as an electron’s infinite distance from the nucleus, a larger negative number describes a lower energy
level. Although this may be confusing, it makes sense that an energy change would be a positive number.
 1 1 
∆E = –(2.180x10–18 J)  2 − 2  = –3.027778x10–19 = 3.028x10–19 J
2 3 
hc
c) E =
λ

λ (m) =
hc
=
(
6.626x10−34 J•s 2.9979x108 m/s )(
= 6.56061x10–7 = 6.561x10–7 m
)
E ( −19
3.027778x10 J )
 1 nm 
(
λ (nm) = 6.56061x10−7 m  −9 )
 = 656.061 = 656.1 nm
 10 m 
This is the wavelength for the observed red line in the hydrogen spectrum.

7.63 Plan: When light of sufficient frequency (energy) shines on metal, electrons in the metal break free and a current
flows.
Solution:

7-16
 a) The lines do not begin at the origin because an electron must absorb a minimum amount of energy before it has
enough energy to overcome the attraction of the nucleus and leave the atom. This minimum energy is the energy
of photons of light at the threshold frequency.
b) The lines for K and Ag do not begin at the same point. The amount of energy that an electron must absorb to
leave the K atom is less than the amount of energy that an electron must absorb to leave the Ag atom, where the
attraction between the nucleus and outer electron is stronger than in a K atom.
c) Wavelength is inversely proportional to energy. Thus, the metal that requires a larger amount of energy to be
absorbed before electrons are emitted will require a shorter wavelength of light. Electrons in Ag atoms require
more energy to leave, so Ag requires a shorter wavelength of light than K to eject an electron.
d) The slopes of the line show an increase in kinetic energy as the frequency (or energy) of light is increased.
Since the slopes are the same, this means that for an increase of one unit of frequency (or energy) of light, the
increase in kinetic energy of an electron ejected from K is the same as the increase in the kinetic energy of an
electron ejected from Ag. After an electron is ejected, the energy that it absorbs above the threshold energy
becomes the kinetic energy of the electron. For the same increase in energy above the threshold energy, for either
K or Ag, the kinetic energy of the ejected electron will be the same.

hc ( 6.626x10 −34
J•s)(3.00x108 m/s  1 nm  ) –19
7.64 a) E = =  −9  = 2.8397x10 J
λ 700. nm  10 m 
This is the value for each photon, that is, J/photon.

(
Number of photons = 2.0x10−17 J 

 2.8397x10
)
1 photon 
−19 
J
= 70.430 = 70. photons

hc (6.626x10 −34
J•s)(3.00x108 m/s  1nm  ) –19
b) E = =  −9  = 4.18484x10 J
λ 475. nm  10 m 
This is the value for each photon, that is, J/photon.

( 
Number of photons = 2.0x10−17 J 

1 photon
4.18484x10
)
−19 
J


= 47.7916 = 48 photons

7.65 Determine the wavelength:

λ = 1/(1953 cm–1) = 5.1203277x10–4 cm
 10−2 m   1 nm 
(
λ (nm) = 5.1203277x10−4 cm  )
 1 cm   10−9 m 
= 5120.3277 = 5.120x103 nm
 
 10−2 m   1 Å 
(
λ (Å) = 5.1203277x10−4 cm  )
 1 cm   10−10 m 
= 51203.277 = 5.120x104 Å
  
2.9979x10 m/s  1 cm   1 Hz 
8
ν = c/λ =  
13
 = 5.8548987x10 = 5.855x10 Hz
13

5.1203277x10−4 cm  10−2 m   1 s −1 

7.66 Plan: The Bohr model has been successfully applied to predict the spectral lines for one-electron species other
than H. Common one-electron species are small cations with all but one electron removed. Since the problem
specifies a metal ion, assume that the possible choices are Li2+ or Be3+. Use the relationship E = hν to convert the
 Z2 
( )
frequency to energy and then solve Bohr’s equation E = 2.18x10−18 J  2  to verify if a whole number for Z
n 
 
can be calculated. Recall that the negative sign is a convention based on the zero point of the atom’s energy; it is
deleted in this calculation to avoid taking the square root of a negative number.
Solution:
The highest energy line corresponds to the transition from n = 1 to n = ∞.
E = hν = (6.626x10–34 J•s) (2.961x1016 Hz) (s–1/Hz) = 1.9619586x10–17 J

7-17
  Z2 
(
E = 2.18x10−18 J  2
n )  Z = charge of the nucleus
 
En 2 1.9619586x10−17 (12 )
Z2 = = = 8.99998
2.18x10 −18 J 2.18x10−18 J
Then Z2 = 9 and Z = 3.
Therefore, the ion is Li2+ with an atomic number of 3.

7.67 a) Electron: λ =
h
=
( 6.626 x10 J•s )  kg•m /s  = 2.139214x10 = 2.1x10
−34 2 2
–10 –10
m
 
mu
( 9.11x10 kg )  3.4x10 ms   J 
−31 6

Proton: λ =
h
=
( 6.626x10 J•s )  kg•m /s  = 1.16696x10 = 1.2x10 m
−34 2 2
–13 –13
 
mu
(1.67x10 kg )  3.4x10 ms   J 
−27 6

b) E = 1/2mu2 therefore u2 = 2E/m

2E
u=
m

Electron: u =
( 
)
2 2.7x10−15 J  kg•m 2 /s2  7
 = 7.6991x10 m/s
( 9.11x10−31 kg  J ) 

2 ( 2.7x10 J )  kg•m /s 
−15 2 2
6
Proton: u =   = 1.7982x10 m/s
(1.67x10 kg )  J 
−27

Electron: λ =
h
=
( 6.626x10 J•s ) 
−34
 kg•m /s 
 = 9.44698x10
2 2
–12
= 9.4x10–12 m
m  
mu
( 9.11x10 kg ) 
 −31
7.6991x10
s 
J  7

Proton: λ =
h
=
( 6.626x10 J•s ) 
−34
 kg•m /s 
 = 2.20646 x 10
2 2
–13
= 2.2 x 10–13 m
m  
mu
(1.67x10 kg ) 1.7982x10 s 
 −27 J  6

7.68 Plan: The electromagnetic spectrum shows that the visible region goes from 400 to 750 nm (4000 Å to 7500 Å).
Thus, wavelengths b, c, and d are for the three transitions in the visible series with n final = 2. Wavelength a is in
the ultraviolet region of the spectrum and the ultraviolet series has n final = 1. Wavelength e is in the infrared region
of the spectrum and the infrared series has n final = 3. Use the Rydberg equation to find the n initial for each line.
Convert the wavelengths from Å to units of m.
Solution:
n = ? → n = 1; λ = 1212.7 Å (shortest λ corresponds to the largest ∆E)
 10−10 m 
λ (m) = (1212.7 ) = 1.2127x10–7 m
 1  
 
 
1
λ
(
= 1.096776x107 m −1 )  n1 2
−
1
n22

 1 
7 −1  1 1 


1
−7

(
 = 1.096776x10 m  2 − 2 
 1.2127x10 m 
)
1 n2 

7-18
 1 1 
0.7518456 =  2 − 2 
1
 n2 
 1 
 2  = 1 – 0.7518456
 n2 
 1 
 2  = 0.2481544
 n2 
n 2 = 2 for line (a) (n = 2 → n = 1)
n = ? → n = 3; λ = 10,938 Å (longest λ corresponds to the smallest ∆E)
 10−10 m 
λ (m) = (10,938 ) = 1.0938x10–6 m
 1  
 
 1 1 
1
λ
( )
= 1.096776x107 m −1  2 − 2 
 n2 
 n1
 


1
−6

( 7 −1
 = 1.096776x10 m
 1.0938x10 m 
)  31
2
−
1
n22 
 
 1 1 
0.083357397 =  2 − 2 
3 n2 

1
0.083357397 = 0.111111111 −
n22
 1 
 2  = 0.11111111 – 0.083357396
 n2 
 1 
 2  = 0.0277537151
 n2 
n22 =36.03121
n 2 = 6 for line (e) (n = 6 → n = 3)
For the other three lines, n 1 = 2.
For line (d), n 2 = 3 (largest λ → smallest ∆E).
For line (b), n 2 = 5 (smallest λ → largest ∆E).
For line (c), n 2 = 4.

hc hc
7.69 E= thus λ =
λ E

a) λ (nm) =
hc ( )(
6.626x10−34 J•s 3.00x108 m/s  1 nm  )
=  −9  = 432.130 = 432 nm
E 4.60x10−19 J  10 m 

b) λ (nm) =
hc ( )(
6.626x10−34 J•s 3.00x108 m/s  1 nm  )
=  −9  = 286.4265 = 286 nm
E 6.94x10−19 J  10 m 

c) λ (nm) =
hc ( )(
6.626x10−34 J•s 3.00x108 m/s  1 nm  )
=  −9  = 450.748 = 451 nm
E 4.41x10−19 J  10 m 

7.70 Index of refraction = c/v; v = c/(index of refraction)

a) Water v = c/(index of refraction) = (3.00x108 m/s)/(1.33) = 2.2556x108 = 2.26x108 m/s
b) Diamond v = c/(index of refraction) = (3.00x108 m/s)/(2.42) = 1.239669x108 = 1.24x108 m/s

7-19
7.71 Extra significant figures are necessary because of the data presented in the problem.
He–Ne λ = 632.8 nm
Ar ν = 6.148x1014 s–1
Ar–Kr E = 3.499x10–19 J
Dye λ = 663.7 nm
Calculating missing λ values:
Ar λ = c/ν = (2.9979x108 m/s)/(6.148x1014 s–1) = 4.8762199x 10–7 = 4.876x10–7 m
Ar–Kr λ = hc/E = (6.626x10–34 J•s) (2.9979x108 m/s)/(3.499x10–19 J) = 5.67707x10–7 = 5.677x10–7 m
Calculating missing ν values:
He–Ne ν = c/λ = (2.9979x108 m/s)/[632.8 nm (10–9 m/nm)] = 4.7375 x 1014 = 4.738 x 1014 s–1
Ar–Kr ν = E/h = (3.499x10–19 J)/(6.626x10–34 J•s) = 5.28071x1014 = 5.281x1014 s–1
Dye ν = c/λ = (2.9979x108 m/s)/[663.7 nm (10–9 m/nm)] = 4.51695x1014 = 4.517x1014 s–1
Calculating missing E values:
He–Ne E = hc/λ = [(6.626x10–34 J•s)(2.9979x108 m/s)]/[632.8 nm (10–9 m/nm)]
= 3.13907797x10–19 = 3.139x10–19 J
Ar E = hν = (6.626x10–34 J•s)(6.148x1014 s–1) = 4.0736648x10–19 = 4.074x10–19 J
Dye E = hc/λ = [(6.626x10–34 J•s)(2.9979x108 m/s)]/[663.7 nm (10–9 m/nm)]
= 2.99293x10–19 = 2.993x10–19 J
The colors may be predicted from Figure 7.3 and the frequencies.
He–Ne ν = 4.738x1014 s–1 Orange
Ar ν = 6.148x1014 s–1 Green
Ar–Kr ν = 5.281x1014 s–1 Yellow
Dye ν = 4.517x1014 s–1 Red

7.72 Plan: Allowed values of quantum numbers: n = positive integers; l = integers from 0 to n – 1;
m l = integers from – l through 0 to + l.
Solution:
a) The l value must be at least 1 for m l to be – 1, but cannot be greater than n – 1 = 3 –1 = 2. Increase the l value
to 1 or 2 to create an allowable combination.
b) The l value must be at least 1 for m l to be +1, but cannot be greater than n – 1 = 3 – 1 = 2. Decrease the l value
to 1 or 2 to create an allowable combination.
c) The l value must be at least 3 for m l to be +3, but cannot be greater than n – 1 = 7 – 1 = 6. Increase the l value
to 3, 4, 5, or 6 to create an allowable combination.
d) The l value must be at least 2 for m l to be –2, but cannot be greater than n – 1 = 4 – 1 = 3. Increase the l value
to 2 or 3 to create an allowable combination.

 1 1 
7.73
1
λ
(  )
= 1.096776x107 m −1  2 − 2 
n2 
 n1
 1 nm   
( )  11
1 1
= 1.096776x107 m −1 − 
94.91 nm  10−9 m 
a) 2
 n22 
1 1 
0.9606608 =  2 − 2 
1
 n2 
n2 = 5
 1 nm   
b)
1
  =
1281 nm  10−9 m 
(1.096776x10 m )  n1
7 −1
2
−
1
52

 1 
 1 1 
0.071175894 =  2 − 2 
n 5 
 1

7-20
 n1 = 3
c)
1
λ
( 1 1 
= 1.096776x107 m −1  2 − 2 
1 3 
)
1
= 9.74912x106 m–1
λ

(
λ = 1.02573x10−7 m  )  101 nmm  = 102.573 = 102.6 nm
−9

7.74 Plan: Ionization occurs when the electron is completely removed from the atom, or when n final = ∞. We can
use the equation for the energy of an electron transition to find the quantity of energy needed to remove
completely the electron, called the ionization energy (IE). To obtain the ionization energy per mole of species,
multiply by Avogadro’s number. The charge on the nucleus must affect the IE because a larger nucleus would
exert a greater pull on the escaping electron. The Bohr equation applies to H and other one-electron species. Use
the expression to determine the ionization energy of B4+. Then use the expression to find the energies of the
hc
transitions listed and use E = to convert energy to wavelength.
λ
Solution:
 Z2 
(
a) E = −2.18x10−18 J  2
n )  Z = atomic number
 
 1  2
(
∆E = −2.18x10−18 J  2
n )
− 2
1
 Z
 final ninitial 
 1 1  2  6.022x1023 
(
∆E = −2.18x10−18 J  2 − 2 )
∞ Z 
ninitial   1 mol 


= (1.312796x106) Z2 for n = 1
b) In the ground state n = 1, the initial energy level for the single electron in B4+. Once ionized, n = ∞ is the final
energy level.
Z = 5 for B4+.
∆E = IE = (1.312796x106) Z2 = (1.312796x106 J/mol)(52) = 3.28199x107 = 3.28x107 J/mol
c) n final = ∞, n initial = 3, and Z = 2 for He+.
 1 1  2 −18  1 1  2
(
∆E = −2.18x10−18 J  2 − 2 )
n (
 Z = −2.18x10 J  2 − 2  2 = 9.68889x10 J
∞
)–19

 final ninitial   3 
hc
E=
λ

λ (m) =
hc
=
(
6.626x10−34 J•s 3.00x108 m/s)( = 2.051628x10–7 m
)
−19
E 9.68889x10 J
 1 nm 
( )
λ (nm) = 2.051628x10−7 m  −9  = 205.1628 = 205 nm
 10 m 
d) n final = ∞, n initial = 2, and Z = 4 for Be3+.
 1 1  2 −18  1 1  2
(
∆E = −2.18x10−18 J  2 − 2 )
∞ (
 Z = −2.18x10 J  2 − 2  4 = 8.72x10 J
∞
)
–18

 n initial   2 

λ (m) =
hc
=
(6.626x10 −34
)(
J•s 3.00x108 m/s ) = 2.279587x10 –8
m
−18
E 8.72x10 J
 1 nm 
( )
λ (nm) = 2.279587x10−8 m  −9  = 22.79587 = 22.8 nm
 10 m 

7-21
7.75 a) Orbital D has the largest value of n, given that it is the largest orbital.
b) l = 1 indicates a p orbital. Orbitals A and C are p orbitals. l = 2 indicates a d orbital. Orbitals B and D are d
orbitals.
c) In an atom, there would be four other orbitals with the same value of n and the same shape as orbital B.
There would be two other orbitals with the same value of n and the same shape as orbital C.
d) Orbital D has the highest energy and orbital C has the lowest energy.

7.76 Plan: Use the values and the equation given in the problem to calculate the appropriate values.
Solution:
n2 h2 ε 0
a) r n =
π me e2
2 C2 
(
12 6.626x10−34 J•s  8.854x10−12 )
J•m   kg•m 2 /s2 
 –11 –11
r1 =   = 5.2929377x10 = 5.293x10 m
( )( )
2
π 9.109x10−31 kg 1.602x10−19 C  J 

2 C2 
(
102 6.626x10−34 J•s  8.854x10−12  )
J•m   kg•m 2 /s2 
 –9 –9
b) r 10 =   = 5.2929377x10 = 5.293x10 m
( )( )
2
π 9.109x10−31 kg 1.602x10−19 C  J 

n2 h2 ε 0
7.77 a) r n =
π me e2
2 C2 
(
32 6.626x10−34 J•s  8.854x10−12 ) 
J•m   kg•m 2 /s2 
 –10 –10
r3 =   = 4.76364x10 = 4.764x10 m
( )( )
2
π 9.109x10−31 kg 1.602x10−19 C  J 
b) Z = 1 for an H atom
 Z2   
( ) ( )  13
2
E n = −2.18x10−18 J  2 −18
 = −2.18x10 J
–19 –19
 = – 2.42222x10 = – 2.42x10 J
n 2
   
c) Z = 3 for a Li atom
 Z2   32 
( ) (
E n = −2.18x10−18 J  2  = −2.18x10−18 J  2  = – 2.18x10–1
n  3  )
   
d) The greater number of protons in the Li nucleus results in a greater interaction between the Li nucleus and its
electrons. Thus, the energy of an electron in a particular orbital becomes more negative with increasing atomic
number.

7.78 Plan: Refer to Chapter 6 for the calculation of the amount of heat energy absorbed by a substance from its
specific heat capacity and temperature change (q = c x mass x ∆T). Using this equation, calculate the energy
absorbed by the water. This energy equals the energy from the microwave photons. The energy of each photon
can be calculated from its wavelength: E = hc/λ. Dividing the total energy by the energy of each photon gives the
number of photons absorbed by the water.
Solution:
q = c x mass x ∆T
q = (4.184 J/g°C)(252 g)(98 – 20.)°C = 8.22407x104 J

E=
hc
=
( 6.626x10 −34
)(
J•s 3.00x108 m/s ) = 1.28245x10 –23
J/photon
−2
λ 1.55x10 m

7-22
 (
Number of photons = 8.22407x104 J 
 1 photon
)
−23 
 1.28245x10 J 

= 6.41278x1027 = 6.4x1027 photons

7.79 One sample calculation will be done using the equation in the book:
3 3
−r
 1  1  2 −r
 1  1  2 −r
ψ=    e a0
=    e a0
= 1.465532x10–3 e a0

 π   a0   π  52.92 pm 
For r = 50 pm:
−r −50
ψ = 1.465532x10–3 e a0 = 1.465532x10–3 e 52.92 = 5.69724x10–4
ψ2 = (5.69724x10–4)2 = 3.24585x10–7
4πr2ψ2 = 4π(50)2(3.24585x10–7) = 1.0197x10–2
r (pm) ψ (pm–3/2) ψ2 (pm–3) 4πr2ψ2 (pm–1)
–3 –6
0 1.47x10 2.15x10 0
50 0.570x10–3 0.325x10–6 1.02x10–2
–3 –6
100 0.221x10 0.0491x10 0.616x10–2
–3 –6
200 0.0335x10 0.00112x10 0.0563x10–2

The plots are similar to Figure 7.17A in the text.

7.80 Plan: In general, to test for overlap of the two series, compare the longest wavelength in the “n” series with the
shortest wavelength in the “n+1” series. The longest wavelength in any series corresponds to the transition
between the n 1 level and the next level above it; the shortest wavelength corresponds to the transition between the n 1
1  1 1 
level and the n = ∞ level. Use the relationship = R  2 − 2  to calculate the wavelengths.
λ n n2 
 1
Solution:
 1 1   1 1 
1
λ   (
= R  2 − 2  = 1.096776x107 m −1  2 − 2 
 )
n2 
 n1 n2   n1
a) The overlap between the n 1 = 1 series and the n 1 = 2 series would occur between the longest wavelengths for
n 1 = 1 and the shortest wavelengths for n 1 = 2.
Longest wavelength in n 1 = 1 series has n 2 equal to 2.
1
λ
( 1
) 1 
= 1.096776x107 m −1  2 − 2  = 8,225,820 m–1
1 2 
1
λ= −1
= 1.215684272x10–7 = 1.215684x10–7 m
8,225,820 m
Shortest wavelength in the n 1 = 2 series:

7-23
1
λ
( )
= 1.096776x107 m −1  2 −
 1
2
1 
∞2 
 = 2,741,940 m
–1

1
λ= = 3.647052817x10–7 = 3.647053x10–7 m
2,741,940 m −1
Since the longest wavelength for n 1 = 1 series is shorter than shortest wavelength for n 1 = 2 series, there
is no overlap between the two series.
b) The overlap between the n 1 = 3 series and the n 1 = 4 series would occur between the longest wavelengths for
n 1 = 3 and the shortest wavelengths for n 1 = 4.
Longest wavelength in n 1 = 3 series has n 2 equal to 4.
1
λ
( )  1 1 
= 1.096776x107 m −1  2 − 2  = 533,155 m–1
3 4 
1
λ= = 1.875627163x10–6 = 1.875627x10–6 m
533,155 m −1
Shortest wavelength in n 1 = 4 series has n 2 = ∞.
1
λ
( )
= 1.096776x107 m −1  2 −
 1
 4 ∞
1 
2 

= 685,485 m–1

1
λ= = 1.458821127x10 = 1.458821x10–6 m
–6

685,485 m −1
Since the n 1 = 4 series shortest wavelength is shorter than the n 1 = 3 series longest wavelength, the series do
overlap.
c) Shortest wavelength in n 1 = 5 series has n 2 = ∞.
1
λ
( )
= 1.096776x107 m −1  2 −
 1
5
1 
∞ 2 
= 438,710.4 m–1

1
λ= −1
= 2.27940801x10–6 = 2.279408x10–6 m
438,710.4 m
Calculate the first few longest lines in the n 1 = 4 series to determine if any overlap with the shortest wavelength
in the n 1 = 5 series:
For n 1 = 4, n 2 = 5:
1
λ
( )  1 1 
= 1.096776x107 m −1  2 − 2  = 246,774.6 m–1
4 5 
1
λ= = 4.052281x10–6 m
246,774.6 m −1
For n 1 = 4, n 2 = 6:
1
λ
( )  1 1 
= 1.096776x107 m −1  2 − 2  = 380,825 m–1
4 6 
1
λ= = = 2.625878x10–6 m
380,825 m −1
For n 1 = 4, n 2 = 7:
1
λ
( )  1 1 
= 1.096776x107 m −1  2 − 2  = 461,653.2 m–1
4 7 
1
λ= −1
= 2.166128x10–6 m
461,653.2 m
The wavelengths of the first two lines of the n 1 = 4 series are longer than the shortest wavelength in the n 1 = 5
series. Therefore, only the first two lines of the n 1 = 4 series overlap the n 1 = 5 series.
d) At longer wavelengths (i.e., lower energies), there is increasing overlap between the lines from different series
(i.e., with different n 1 values). The hydrogen spectrum becomes more complex, since the lines begin to merge into a
more-or-less continuous band, and much more care is needed to interpret the information.

7-24
7.81 a) The highest frequency would correspond to the greatest energy difference. In this case, the greatest energy
difference would be between E 3 and E 1 .
∆E = E 3 – E 1 = hν = (– 15x10–19 J) – (– 20x10–19 J) = 5x10–19 J
ν = ∆E/h = (5x10–19 J)/(6.626x10–34 J•s) = 7.54603x1014 = 8x1014 s–1
λ = c/ν = (3.00x108 m/s)/(7.54603x1014 s–1) = 3.97560x10–7 = 4x10–7 m
b) The ionization energy (IE) is the same as the reverse of E 1 . Thus, the value of the IE is 20x10–19 J/atom.
IE = (20x10–19 J/atom)(1kJ/103 J)(6.022x1023 atoms/mol) = 1204.4 = 1.2x103 kJ/mol
c) The shortest wavelength would correspond to an electron moving from the n = 4 level to the highest level
available in the problem (n = 6).
∆E = E 6 – E 4 = hc/λ = (– 2x10–19 J) – (– 11x10–19 J) = 9x10–19 J

λ = hc/∆E =
( 6.626x10 −34
)( )
J•s 3.00x108 m/s  1 nm  2
 −9  = 220.867 = 2x10 nm
( −19
9x10 J )  10 m 

7.82 Plan: The energy differences sought may be determined by looking at the energy changes in steps. The
hc
wavelength is calculated from the relationship λ = .
E
Solution:
a) The difference between levels 3 and 2 (E 32 ) may be found by taking the difference in the energies for the 3 → 1
transition (E 31 ) and the 2 → 1 transition (E 21 ).
E 32 = E 31 – E 21 = (4.854x10–17 J) – (4.098x10–17 J) = 7.56x10–18 J

λ=
hc
=
( )(
6.626x10−34 J•s 3.00x108 m/s )
= 2.629365x10–8 = 2.63x10–8 m
E (
7.56x10−18 J )
b) The difference between levels 4 and 1 (E 41 ) may be found by adding the energies for the 4 → 2 transition (E 42 )
and the 2 → 1 transition (E 21 ).
E 41 = E 42 + E 21 = (1.024x10–17 J) + (4.098x10–17 J) = 5.122x10–17 J

λ=
hc
=
( )(
6.626x10−34 J•s 3.00x108 m/s )
= 3.88091x10–9 = 3.881x10–9 m
E (
5.122x10−17 J )
c) The difference between levels 5 and 4 (E 54 ) may be found by taking the difference in the energies for the 5 → 1
transition (E 51 ) and the 4 → 1 transition (see part b)).
E 54 = E 51 – E 41 = (5.242x10–17 J) – (5.122x10–17 J) = 1.2x10–18 J

λ=
hc
=
( )(
6.626x10−34 J•s 3.00x108 m/s )
= 1.6565x10–7 = 1.66x10–7 m
E (
1.2x10−18 J )
7.83 a) A dark green color implies that relatively few photons are being reflected from the leaf. A large fraction of the
photons is being absorbed, particularly in the red region of the spectrum. A plant might adapt in this way when
photons are in short supply — i.e., in conditions of low light intensity.
b) An increase in the concentration of chlorophyll, the light-absorbing pigment, would lead to a darker green
color (and vice versa).

7.84 Plan: For part a), use the equation for kinetic energy, E k = ½mu2. For part b), use the relationship E = hc/λ to find
the energy of the photon absorbed. From that energy subtract the kinetic energy of the dislodged electron to
obtain the work function.
Solution:
a) The energy of the electron is a function of its speed leaving the surface of the metal. The mass of the electron is
9.109x10–31 kg.
2 
1
E k = mu2 =
2
1
2 ( )(
9.109x10−31 kg 6.40x105 m/s 
J
)
2 2 
= 1.86552x10–19 = 1.87x10–19 J
 kg•m /s 

7-25
 b) The minimum energy required to dislodge the electron (φ) is a function of the incident light. In this example,
the incident light is higher than the threshold frequency, so the kinetic energy of the electron, E k , must be
subtracted from the total energy of the incident light, hν, to yield the work function, φ. (The number of significant
figures given in the wavelength requires more significant figures in the speed of light.)
 10−9 m 
λ (m) = ( 358.1 nm )  = 3.581x10–7 m
 1nm 
 

E = hc/λ =
( 6.626x10 J•s )( 2.9979x10
−34 8
m/s ) = 5.447078x10 –19
J
( 3.581x10 m )
−7

Φ = hν – E k = (5.447078x10–19 J) – (1.86552x10–19 J) = 3.581558x10–19 = 3.58x10–19 J

7.85 a) λ = h/mu =
(6.626x10 J•s ) −34
 kg•m 2 /s2 

–8
 = 1.322568x10 m
(9.109x10 kg )  5.5x10
−31 4 m
s 
J 

Smallest object = λ/2 = (1.322568x10–8 m)/2 = 6.61284x10–9 = 6.6x10–9 m

b) λ = h/mu =
(6.626x10 J•s )
−34
 kg•m 2 /s2 

–11
 = 2.424708x10 m
(9.109x10 kg )  3.0x10
−31 7 m
s 
J 

Smallest object = λ/2 = (2.424708x10–11 m)/2 = 1.212354x10–11 = 1.2x10–11 m

7.86 Plan: Examine Figure 7.3 and match the given wavelengths to their colors. For each salt, convert the mass of salt
to moles and multiply by Avogadro’s number to find the number of photons emitted by that amount of salt
hc
(assuming that each atom undergoes one-electron transition). Use the relationship E = to find the energy of
λ
one photon and multiply by the total number of photons for the total energy of emission.

Solution:
a) Figure 7.3 indicates that the 641 nm wavelength of Sr falls in the red region and the 493 nm wavelength of Ba
falls in the green region.
b) SrCl 2
 1 mol SrCl 2   6.022x1023 photons 
Number of photons = ( 5.00 g SrCl 2 )   
22
 = 1.8994449x10 photons
 158.52 g SrCl 2   1 mol SrCl 2 
 10−9 m 
λ (m) = ( 641 nm )  –7
 = 6.41x10 m
 1nm
 

hc ( 6.626x10 −34
)( )
J•s 3.00x108 m/s  1 kJ 
–22
E photon = =  3  = 3.10109x10 kJ/photon
λ 6.41x10−7 m  10 J 
 3.10109x10−22 kJ 
(
E total = 1.8994449x1022 photons 
) 1 photon
 = 5.89035 = 5.89 kJ
 
BaCl 2
 1 mol BaCl 2   6.022x1023 photons 
Number of photons = ( 5.00 g BaCl 2 )    = 1.44620557x1022 photons

 208.2 g BaCl 2  1 mol BaCl 2 
 10−9 m 
λ (m) = ( 493 nm )  –7
 = 4.93x10 m
 1nm
 

7-26
 hc ( 6.626x10 −34
)( )
J•s 3.00x108 m/s  1 kJ 
–22
E photon = = −7  3  = 4.0320487x10 kJ/photon
λ 4.93x10 m  10 J 
 4.0320487x10−22 kJ 
(
E total = 1.44620557x1022 photons 
 )
1 photon
 = 5.83117 = 5.83 kJ
 
7.87 a) The highest energy line corresponds to the shortest wavelength. The shortest wavelength line is given by
 1 1   1 1 
1
λ n n2 
(
= R  2 − 2  = 1.096776x107 m −1  2 − 2 
n )
n2 
 1  1
 1 nm   
1

3282 nm  10−9 m 
( 7
 = 1.096776x10 m
−1
)  n1 2
−
1
∞2

 1 
304,692 m–1 = (1.096776x107 m–1) (1/n2)
1/n2 = 0.0277807
n=6
b) The lowest energy line corresponds to the longest wavelength. The longest wavelength line is given by
 1 
1
λ
(
= 1.096776x107 m −1  2 −
 n1
) ( n
1
+ 1)

2 
 1 
 1 nm   1 
( )
1 1
 −9  = 1.096776x107 m −1  2 − 
7460 nm  10 m  n
 1 ( n1 + 1) 
2

 1 
(
134,048 m–1 = 1.096776x107 m −1  2 −
 n1
) ( n
1
+ 1)

2 
 1 
 1 1 
0.0122220 =  2 − 
 n1
 ( n1 + 1) 2 

Rearranging and solving this equation for n 1 yields n 1 = 5. (You and your students may well need to resort to trial-
and-error solution of this equation!)

7.88 Plan: Examine Figure 7.3 to find the region of the electromagnetic spectrum in which the wavelength lies.
Compare the absorbance of the given concentration of Vitamin A to the absorbance of the given amount of fish-
liver oil to find the concentration of Vitamin A in the oil.
Solution:
a) At this wavelength the sensitivity to absorbance of light by Vitamin A is maximized while minimizing
interference due to the absorbance of light by other substances in the fish-liver oil.
b) The wavelength 329 nm lies in the ultraviolet region of the electromagnetic spectrum.
c) A known quantity of vitamin A (1.67x10–3 g) is dissolved in a known volume of solvent (250. mL) to give a
standard concentration with a known response (1.018 units). This can be used to find the unknown quantity of
Vitamin A that gives a response of 0.724 units. An equality can be made between the two concentration-to-
absorbance ratios.
 1.67x10−3 g 
Concentration (C 1 , g/mL) of Vitamin A =  = 6.68x10–6 g/mL Vitamin A
 250. mL 
 
Absorbance (A 1 ) of Vitamin A = 1.018 units.
Absorbance (A 2 ) of fish-liver oil = 0.724 units
Concentration (g/mL) of Vitamin A in fish-liver oil sample = C 2
A1 A
= 2
C1 C2

7-27
 C2 =
A2C1
=
(
( 0.724 ) 6.68x10−6 g/mL
= 4.7508x10–6 g/mL Vitamin A
)
A1 (1.018 )
 4.7508x10−6 g Vitamin A 
Mass (g) of Vitamin A in oil sample = ( 500. mL oil )  –3
 = 2.3754x10 g Vitamin A
 1 mL oil
 

Concentration of Vitamin A in oil sample =

( 2.3754x10 g ) = 1.92808x10
−3
–2
= 1.93x10–2 g Vitamin A/g oil
( 0.1232 g Oil )

λ = hc/E =
( 6.626x10 J•s )( 3.00x10
−34 8
)
m/s  1 nm 
7.89  −9  = 261.897 = 262 nm
( 7.59x10 J ) −19
 10 m 
Silver is not a good choice for a photocell that uses visible light because 262 nm is in the ultraviolet region.

7.90 Mr. Green must be in the dining room where green light (520 nm) is reflected. Lower frequency, longer
wavelength light is reflected in the lounge and study. Both yellow and red light have longer wavelengths than
green light. Therefore, Col. Mustard and Ms. Scarlet must be in either the lounge or study. The shortest
wavelengths are violet. Prof. Plum must be in the library. Ms. Peacock must be the murderer.

1
7.91 Ek = mv2
2

Ek 4.71x10−15 J  kg•m 2 /s2  8

v= =   = 1.01692775x10 m/s
1
2
m 1
2 ( 9.109x10−31 kg  J ) 

λ = h/mv =
( 6.626x10 J•s ) −34
 kg•m 2 /s2

 –12 –12
 = 7.15304x10 = 7.15x10 m
m  
( 9.109x10 kg ) 1.01692775x10
−31 8
s 
J 

7.92 Plan: First find the energy in joules from the light that shines on the text. Each watt is one joule/s for a total
hc
of 75 J; take 5% of that amount of joules and then 10% of that amount. Use E = to find the energy of one
λ
photon of light with a wavelength of 550 nm. Divide the energy that shines on the text by the energy of one
photon to obtain the number of photons.
Solution:
The amount of energy is calculated from the wavelength of light:
 10−9 m 
λ (m) = ( 550 nm )  = 5.50x10–7 m
 1 nm 
 

E=
hc
=
(6.626x10 −34
)(
J•s 3.00x108 m/s ) = 3.614182x10 –19
J/photon
−7
λ 5.50x10 m
 1 J/s 
Amount of power from the bulb = ( 75 W )   = 75 J/s
1W 
 5% 
Amount of power converted to light = ( 75 J/s )   = 3.75 Js
 100% 
 10% 
Amount of light shining on book = ( 3.75 J/s )   = 0.375 J/s
 100% 
 0.375 J   1 photon 
Number of photons:   −19 
= 1.0376x1018 = 1.0x1018 photons/s
 s  3.614182x10 J 

7-28
7.93 a) Sodium ions emit yellow-orange light, and potassium ions emit violet light.
b) The cobalt glass filter absorbs the yellow-orange light, while the violet light passes through.
c) Sodium salts used as the oxidizing agents would emit intense yellow-orange light which would obscure the
light emitted by other salts in the fireworks.

7.94 a) 6CO 2 (g) + 6H 2 O(l) → C 6 H 12 O 6 (s) + 6O 2 (g)

∆H rxn = {(1 mol) ∆H f [C 6 H 12 O 6 ] + (6 mol) ∆H f [O 2 ]} – {(6 mol) ∆H f [CO 2 ] + (6 mol) ∆H f [H 2 O]}
∆H rxn = [–1273.3 kJ + 6(0.0 kJ)] – [6(–393.5 kJ) + 6(–285.840 kJ)] = 2802.74 = 2802.7 kJ
6CO 2 (g) + 6H 2 O(l) → C 6 H 12 O 6 (s) + 6O 2 (g) ∆H rxn = 2802.7 kJ (for 1.00 mol C 6 H 12 O 6 )

b) E = hc/λ =
( 6.626x10 −34
)( )
J•s 3.00x108 m/s  1 nm 
–19
 −9  = 2.9232353x10 J/photon
680. nm  10 m 
 103 J   1 photon 
Number of photons = ( 2802.7 kJ )  = 9.5877x1024 = 9.59x1024 photons
 1 kJ   2.9232353x10−19 J 
   

7.95 Plan: In the visible series with n final = 2, the transitions will end in either the 2s or 2p orbitals since those are the
only two types of orbitals in the second main energy level. With the restriction that the angular momentum
quantum number can change by only ±1, the allowable transitions are from a p orbital to 2s (l = 1 to l = 0), from
an s orbital to 2p (l = 0 to l = 1), and from a d orbital to 2p (l = 2 to l = 1). The problem specifies a change in
energy level, so n init must be 3, 4, 5, etc. (Although a change from 2p to 2s would result in a +1 change in l, this is
not a change in energy level.)
Solution:
The first four transitions are as follows:
3s → 2p
3d → 2p
4s → 2p
3p → 2s

7.96 a)

0.9

0.7
Absorbance

0.5

0.3

0.1
0 −5
0 10 20 x 10
Concentration, mol/L
A = kC
k = 4.5x103 M–1 = slope
b) A/k = C = (0.55)/(4.5x103 M–1) = 1.2222x10–4 = 1.2x10–4 M

7-29
Another random document with
no related content on Scribd:
 The power of Ivan Kalita being
once raised by the Tatars’ aid,
and by the re-establishment of
the direct line of succession, and
thoroughly developed by his son
and grandson, Simeon the
Proud and Dmitri Donskoi, it
followed, as a natural
consequence, that he who was
most able to reward and to
punish drew around him, and
retained, the whole of the
nobles. These constituted the
sole strength of the appanaged
princes; their defection,
therefore, completed the
subjugation of the princes.
Dmitri Donskoi
Dmitri Donskoi was, therefore, in
reality sovereign, as is proved
by his treaties with the princes
who held appanages, all of whom he reduced to be his vassals. And,
accordingly, notwithstanding the appanages which he gave to his
sons, and the dissensions which arose out of that error—an error as
yet, perhaps, unavoidable—the attachment of the nobles, for which
we have just assigned a reason, always replaced the legitimate heir
on the throne.
Already, so early as about 1366, the Russian
[1366 a.d.] princes could no longer venture to contend
against their lord paramount by any other
means than by denunciations to the horde; but to what khan could
they be addressed? Discord had created several: what result was to
be hoped from them? Divided among themselves, the Tatar armies
had ceased to be an available force. The journeys to the Golden
Horde, which had originally contributed to keep the Russian princes
in awe, now served to afford them an insight into the weakness of
their enemies. The grand princes returned from the horde with the
confidence that they might usurp with impunity; and their competitors
with envoys and letters, which even they themselves well knew
would be of no avail. It was, then, obvious in Russia, that the only
protecting power was at Moscow: to have recourse to its support
was a matter of necessity. The petty princes could obtain it only by
the sacrifice of their independence; and thus all of them became
vassals to the grand prince Dmitri.
Never did a great man arise more opportunely than this Dmitri. It
was a propitious circumstance, that the dissensions of the Tatars
gave them full occupation during the eighteen years subsequent to
the first three of his reign:[20] this, in the first place, allowed him time
to extinguish the devastating fury of Olgerd the Lithuanian, son of
Gedimin, father of Iagello, and conqueror of all Lithuania, Volhinia,
Smolensk, Kiev, and even of Taurida; secondly, to unite several
principalities with his throne; and lastly, to compel the other princes,
and even the prince of Tver, to acknowledge his paramount
authority.
The contest with the latter was terrible: four times did Dmitri
overcome Michael, and four times did the prince of Tver, aided by his
son-in-law, the great Olgerd, prince of Lithuania, rise again
victorious. In this obstinate conflict, Moscow itself was twice
besieged, and must have fallen, had it not been for its stone walls,
the recent work of the first regency of the Muscovite boyars. But, at
length, Olgerd died; and Dmitri, who, but three years before, could
appear only on his knees at the horde, now dared to refuse the khan
his tribute, and to put to death the insolent ambassador who had
been sent to claim it.
We have seen that, fifty years earlier, a similar instance of temerity
caused the branch of Tver to fall beneath that of Moscow; but times
were changed. The triple alliance of the primate, the boyars, and the
grand prince, had now restored to the Russians a confidence in their
own strength: they had acquired boldness from a conviction of the
power of their grand prince, and from the dissensions of the Tatars.
Some bands of the latter, wandering in Muscovy in search of
plunder, were defeated; at last the Tatars have fled before the
Russians! they are become their slaves, the delusion of their
invincibility is no more!
 The burst of fury which the khan exhibited on learning the murder
of his representative, accordingly served as a signal for the
confederation of all the Russian princes against the prince of Tver.
He was compelled to submit to the grand prince, and to join with him
against the horde.

The Battle of the Don or Kulikovo (1380 a.d.)

Russia now began to feel that there were

[1380 a.d.] three things which were indispensably
necessary to her; the establishment of the direct
succession, the concentration of the supreme power, and the union
of all parties against the Tatars. The movement in this direction was
taken very opportunely; for it happened simultaneously that the
Mongolian chief, Mamai, was also disembarrassed of his civil wars
(1380), and he hastened with all his forces into Russia to re-
establish his slighted authority; but he found the grand prince Dmitri
confronting him on the Don, at the head of the combined Russian
princes and an army of two hundred thousand[21] men. Dmitri put it
to the choice of his troops whether they would go to encounter the
foe, who were encamped at no great distance on the opposite shore
of the river, or remain on this side and wait the attack? With one
voice they declared for going over to the assault. The grand prince
immediately transported his battalions across the river, and then
turned the vessels adrift, in order to cut off all hopes of escaping by
retreat, and inspire his men with a more desperate valour against an
enemy who was three times stronger in numbers. The fight began.
The Russians defended themselves valiantly against the furious
attacks of the Tatars; the hosts of combatants pressed in such
numbers to the field of battle, that multitudes of them were trampled
under foot by the tumult of men and horses. The Tatars, continually
relieved by fresh bodies of soldiers as any part was fatigued by the
conflict, seemed at length to have victory on their side. Nothing but
the impossibility of getting over the river, and the firm persuasion that
death would directly transport them from the hands of the infidel
enemy into the mansions of bliss, restrained the Russians from a
general flight. But all at once, at the very moment when everything
seemed to be lost, a detachment of the grand prince’s army, which
he had stationed as a reserve, and which till now had remained
inactive and unobserved, came up in full force, fell upon the rear of
the Tatars, and threw them into such amazement and terror that they
fled, and left the Russians masters of the field. This momentous
victory, however, cost them dear; thousands lay dead upon the
ground, and the whole army was occupied eight days in burying the
bodies of the dead Russians: those of the Tatars were left uninterred
upon the ground. It was in harmony of this achievement that Dmitri
received his honourable surname of Donskoi.g

Significance of Battle of Kulikovo

The chronicles say that such a battle as that of Kulikovo had never
before been known in Russia; even Europe had not seen the like of it
for a long time. Such bloody conflicts had taken place in the western
half of Europe at the beginning of the so-called Middle Ages, at the
time of the great migration of nations, in those terrible collisions
between European and Asiatic armies; such was the battle of
Châlons-sur-Marne, when the Roman general saved western Europe
from the Huns; such too was the battle of Tours, where the Frankish
leader saved western Europe from the Arabs (Saracens). Western
Europe was saved from the Asiatics, but her eastern half remained
long open to their attacks. Here, about the middle of the ninth
century, was formed an empire which should have served Europe as
a bulwark against Asia; in the thirteenth century this bulwark was
seemingly destroyed, but the foundations of the European empire
were saved in the distant northwest; thanks to the preservation of
these foundations, in a hundred and fifty years the empire
succeeded in becoming unified, consolidated—and the victory of
Kulikovo served as a proof of its strength. It was an omen of the
triumph of Europe over Asia, and has exactly the same signification
in the history of eastern Europe as the victories of Châlons and
Tours have in that of western Europe. It also bears a like character
with them—that of a terrible, bloody slaughter, a desperate struggle
between Europe and Asia, which was to decide the great question in
the history of humanity: which of these two parts of the world was to
triumph over the other.
But the victory of Kulikovo was one of those victories which closely
border upon grievous defeats. When, says the tradition, the grand
prince ordered a count to be made of those who were left alive after
the battle, the boyar Michael Aleksandrovitch reported to him that
there remained in all forty thousand men, while more than four
hundred thousand had been in action. And although the historian is
not obliged to accept the latter statement literally, yet the ratio here
given between the living and the dead is of great importance to him.
Four princes, thirteen boyars, and a monk of the monastery of
Troitsa, were among the slain. It is for this reason that in the
embellished narratives of the defeat of Mamai we see the event
represented on one hand as a great triumph and on the other as a
woeful and lamentable event. There was great joy in Russia, says
the chronicler, but there was also great grief over those slain by
Mamai at the Don; the land of Russia was bereft of all voyevods
(captains) and men and all kinds of warriors, and therefore there was
a great fear throughout all the land of Russia. It was this
depopulation through loss of men that gave the Tatars a short-lived
triumph over the victors of Kulikovo.e

THE DESTRUCTION OF MOSCOW (1382 A.D.)

The immediate and inevitable consequence of

[1382 a.d.] the battle was a sensible reduction of the
Russian army. The numbers that fell before the
Tatars could not be easily or speedily supplied: nor were the means
of a fresh levy accessible. Those districts from which the grand army
was ordinarily recruited had already exhausted their population; all
the remote principalities had contributed in nearly equal proportion,
and the majority of the rest of the empire was composed of persons
who were unaccustomed to the use of arms, having been exclusively
occupied in tillage or commerce. These circumstances, which did not
damp the joy of the victory, or diminish its real importance, presented
to the implacable foe a new temptation for crossing the border. But it
was not until two of the wandering hordes had formed a junction that
the Tatars were able to undertake the enterprise. The preparations
for it occupied them two years. In 1382, the hordes of the Don and
the Volga united, and making a descent upon the frontier provinces
with success, penetrated as far as Moscow. The city had been
previously fortified by the boyars with strong ramparts and iron
gates; and Dmitri, trusting with confidence to the invincibility of the
fortifications, left the capital in the charge of one of his generals,
while he imprudently went into the interior to recruit his army. His
absence in the hour of danger spread consternation amongst the
peaceable part of the inhabitants, particularly the clergy, who relied
upon his energies on the most trying occasions. The metropolitan,
accompanied by a great number of the citizens, left the city upon the
approach of the Tatars. The small garrison that remained made an
ineffectual show on the ramparts, and the Tatars, who might not
otherwise have gained their object, prevailed upon the timidity of the
Russians, who consented to capitulate upon a promise of pardon.
The Tatars observed their pledge in this instance as they had done in
every similar case—by availing themselves of the first opportunity to
violate it. They no sooner entered Moscow than they gave it to the
flames, and massacred every living person they met in the streets.
Having glutted their revenge with a terrible scene of slaughter and
conflagration, they returned home, satisfied with having reduced the
grand princedom once more, after their own fashion, to subjection.
They did not perceive that in this exercise of brutal rage they
strengthened the moral power of Russia, by giving an increased
motive to co-operation, and by rendering the abhorrence of their
yoke still more bitter than before. All they desired was the physical
and visible evidence of superiority; either not heeding, or not
comprehending, the silent and unseen progress of that strength
which combined opinion acquires under the pressure of blind
tyranny.
Dmitri, thus reduced to submission, was compelled once more to
perform the humiliating penance of begging his dignity at the hands
of the khan. Empire had just been within his grasp; he had bound up
the shattered parts of the great mass; he had effected a union of
sentiment, and a bond of co-operation; but in the effort to establish
this desirable end, he had exhausted the means by which alone it
could be perpetuated. Had the Tatars suffered a short period more to
have elapsed before they resumed the work of spoliation, it is not
improbable but that a sufficient force could have been raised to repel
them: but they appeared in considerable numbers, animated by the
wildest passions, at a time when Dmitri was unable to make head
against their approach. The result was unavoidable; and the grand
prince, in suing to be reinstated on the throne from which he was
virtually expelled, merely acquiesced in a necessity which he could
not avert.
But the destruction of Moscow had no effect upon the great
principle that was now in course of development all over the empire.
The grand princedom was still the centre of all the Russian
operations: the grand prince was still the acknowledged authority to
which all the subordinate rulers deferred. While this paramount virtue
of cohesion remained unimpaired, the incursions of the Tatars,
however calamitous in their passing visitations, had no other
influence upon the ultimate destiny of the country than that of
stimulating the latent patriotism of the population, and of convincing
the petty princes, if indeed any further evidence were wanted, of the
disastrous impolicy of wasting their resources in private feuds.

THE DEATH OF DMITRI DONSKOI; HIS PLACE IN HISTORY

The example of Dmitri Donskoi had clearly pointed out the course
which it was the policy of the grand prince to follow; but, in order to
place his own views beyond the reach of speculation, and to enforce
them in as solemn a manner as he could upon his successors, that
prince placed a last injunction upon his son, which he also
addressed in his will to all future grand princes, to persevere in the
lofty object of regeneration by maintaining and strengthening the
domestic alliances of the sovereignty, and resisting the Tatars until
they should be finally driven out of Russia. His reign of twenty-seven
years, crowned with eventful circumstances, and subjected to many
fluctuations, established two objects which were of the highest
consequence to the ultimate completion of the great design. Amidst
all the impediments that lay in his way, or that sprang up as he
advanced, Dmitri continued his efforts to create an order of nobility—
the boyars, who, scattered through every part of the empire, and
surrounding his court on all occasions of political importance, held
the keys of communication and control in their hands, by which the
means of concentration were at all times facilitated. That was one
object, involving in its fulfilment the gradual reduction of the power of
the petty princes, and contributing mainly to the security of the
second object, which was the chief agent of his designs against the
Tatars. In proportion as he won over the boyars to his side, and gave
them an interest in his prosperity, he increased the power of the
grand princedom. These were the elements of his plan: the
progressive concentration of the empire, and the elevation of the
grand princedom to the supreme authority. The checks that he met in
the prosecution of these purposes, of which the descent of the Tatar
army upon Moscow was the principal, slightly retarded, but never
obscured, his progress. The advances that he had made were
evident. It did not require the attestation of his dying instructions to
explain the aim of his life: it was visibly exemplified in the institutions
he bequeathed to his country; in the altered state of society; and in
the general submission of the appanages to a throne which, at the
period of his accession, was shaken to its centre by rebellion.d
In 1389 Dmitri died at the early age of thirty-
[1389 a.d.] nine. His grandfather, his uncle, and his father
had quietly prepared ample means for an open
decisive struggle. Dmitri’s merit consisted in the fact that he
understood how to take advantage of these means, understood how
to develop the forces at his disposal and to impart to them the proper
direction at the proper time. We do not intend to weigh the merits of
Dmitri in comparison with those of his predecessors; we will only
remark that the application of forces is usually more evident and
more resounding than their preparation, and that the reign of Dmitri,
crowded as it was from beginning to end with the events of a
persistent and momentous struggle, easily eclipsed the reigns of his
predecessors with their sparse incidents. Events like the battle of
Kulikovo make a powerful impression upon the imagination of
contemporaries and endure long in the remembrance of their
descendants. It is therefore not surprising that the victor of Mamai
should have been given beside Alexander Nevski so conspicuous a
place amongst the princes of the new northeastern Russia. The best
proof of the great importance attributed to Dmitri’s deeds by
contemporaries is to be found in the existence of a separate
narrative of the exploits of this prince, a separate embellished
biography. Dmitri’s appearance is thus described: “He was strong
and valiant, and great and broad in body, broad shouldered and very
heavy, his beard and hair were black, and very wonderful was his
gaze.” In his biography the severity of his life is extolled, his aversion
to pleasure, his piety, gentleness, his chastity both before and after
marriage; among other things it is said: “Although he was not learned
in books, yet he had spiritual books in his heart.” The end of Dmitri is
thus described: “He fell ill and was in great pain, then it abated, but
he again fell into a great sickness and his groaning came to his
heart, for it touched his inner parts and his soul already drew near to
death.”

Live-fish Merchant

The important consequences of Dmitri’s activity are manifested in

his will and testament, in which we meet with hitherto unheard-of
dispositions. The Moscow prince blesses his eldest son Vasili and
endows him with the grand principality of Vladimir, which he calls his
paternal inheritance. Donskoi no longer fears any rivals to his son,
either from Tver or Suzdal. Besides Vasili, Dmitri had five sons: Iuri,
Andrew, Peter, John, and Constantine; but the two latter were under
age, Constantine having been born only four days before his father’s
death, and the grand prince confides his paternal domain of Moscow
to his four elder sons. In this domain, that is in the town of Moscow
and the districts appertaining to it, Donskoi had ruled over two parts
or shares, the share of his father Ivan and of his uncle Simeon, while
the third share was under the rule of Vladimir Andreevitch, to whom
it now remained. Of his two shares the grand prince left one half to
his eldest son Vasili; the other half was divided in three parts among
the remaining sons, and the other towns of the principality of
Moscow were divided among the four sons; Kolomna went to Vasili,
the eldest, Zvenigorod to Iuri, Mozhaisk to Andrew, Dmitrov to Peter.

THE REIGN OF VASILI-DMITRIEVITCH (1389-1425 A.D.)

From the very commencement of his reign the young son of

Donskoi showed that he would remain true to the traditions of his
father and grandfather. A year after the khan’s ambassador had
placed him on the grand prince’s throne at Vladimir, Vasili set out for
the horde and there purchased a iarlik (letter-patent of the khans) for
the principality of Nijni-Novgorod, which not long before, after many
entreaties had been obtained from the horde by Boris
Constantinovitch. When the letter heard of Vasili’s designs, Boris
called together his boyars and said to them with tears in his eyes:
“My lords and brothers, my boyars and friends! remember your oath
on the cross, remember what you swore to me!” The senior among
his boyars was Vasili Rumianietz, who replied to the prince: “Do not
grieve, my lord prince! we are all faithful to thee and ready to lay
down our heads and to shed our blood for thee.” Thus he spoke to
his prince, but meanwhile he sent to Vasili Dmitrievitch, promising to
give up Boris Constantinovitch to him. On his way back from the
horde, when he had reached Kolomna, Vasili sent from there to Nijni
the ambassador of Toktamish and his own boyars. At first Boris
would not let them enter the town, but Rumianietz said to him: “My
lord prince, the khan’s ambassador and the Muscovite boyars come
here in order to confirm peace and establish everlasting love, but
thou wishest to raise dissensions and war; let them come into the
town; what can they do to thee? we are all with thee.” But as soon as
the ambassador and boyars had entered the town, they ordered the
bells to be rung, assembled the people, and announced to them that
Nijni already belonged to the prince of Moscow. When Boris heard
this he sent for his boyars and said to them: “My lords and brothers,
my beloved drujina! remember your oath on the cross, do not give
me up to my enemies.” But this same Rumianietz replied: “Lord
prince! do not hope in us, we are no longer thine, we are not with
thee, but against thee!” Boris was seized, and when somewhat later
Vasili Dmitrievitch came to Nijni, he placed there his lieutenants; and
Prince Boris, with his wife, children, and partisans, he ordered to be
carried away in chains to various towns and kept in strict
imprisonment.e
The princes of Suzdal, Boris’ nephews, were
[1395-1412 a.d.] banished, and Vasili also acquired Suzdal. Later
on the princes of Suzdal made peace with the
grand prince and received back from him their patrimonial estates,
but from generation to generation they remained dependants of
Moscow and not independent rulers. In 1395 took place an event
which raised the moral importance of Moscow: on account of an
expected invasion of Timur (Tamerlane), which, however, never took
place, Vasili Dmitrievitch ordered to be transported from Vladimir to
Moscow that famous ikon which Andrew had formerly taken from
Kiev to his beloved town of Vladimir; this ikon now served to
consecrate the pre-eminence of Moscow over all other Russian
towns.
Following in the steps of his predecessors, Vasili Dmitrievitch
oppressed Novgorod, but did not however entirely attain to the goal
of his designs. Twice he endeavoured to wrest her Dvinsk colonies
from her, taking advantage of the fact that in the Dvinsk territories a
party had been formed which preferred the rule of the Moscow grand
prince to that of Grand Novgorod. The people of Novgorod were
fortunate in defending their colonies, but they paid dearly for it: the
grand prince laid waste the territory of Novgorod, and ordered some
of the inhabitants who had killed a partisan of his at Torzhok to be
strangled; but worse than all, Novgorod itself could not get on
without the grand prince and was obliged to turn to him for help
when another grand prince, namely the Lithuanian, attempted its
conquest.
At that period the horde was so torn up with inward dissensions
that Vasili had not for some years paid tribute to the khan and
regarded himself as independent; but in 1408 an unexpected attack
was made on Moscow by the Tatar prince Edigei, who like Mamai,
without being khan himself, made those who bore the name of khan
obey him. Vasili Dmitrievitch being off his guard and thinking that the
horde had become weakened, did not take early measures against
his wily adversary, who deceived him by his hypocrisy and pretended
good-will. Like his father he escaped to Kostroma, but provided
better than his father for the defence of Moscow by confiding it to his
brave uncle, Prince Vladimir Andreevitch. The inhabitants
themselves burned their faubourg, and Edigei could not take the
Kremlin, but the horde laid waste many Russian towns and villages.
Moscow now learned that although the horde had no longer the
power to hold Russia in servitude, yet it might still make itself terrible
by its sudden incursions, devastations, and capture of the
inhabitants. Shortly thereafter, in 1412, Vasili went to the horde to do
homage to the new khan Djelalledin, brought him tribute, and made
presents to the Tatar grandees, so that the khan confirmed the grand
principality to the prince of Moscow, although he had previously
intended to bestow it upon the exiled prince of Nijni-Novgorod. The
power of the khans over Russia was now only held by a thread; but
for some time yet the Moscow princes could take advantage of it in
order to strengthen their own authority over Russia and to shelter
their inclinations under the shadow of its ancient might. Meanwhile
they took measures of defence against the Tatar invasions, which
might be all the more annoying because they were directed from
various sides and from various fragments of the crumbling horde. In
the west the Lithuanian power, which had sprung up under Gedimin,
and grown great under Olgerd, had attained to its utmost limits under
Vitovt.
 Strictly speaking, the supreme authority over Lithuania and the
part of Russia in subjection to it belonged to Iagello, king of Poland;
but Lithuania was governed independently in the quality of viceroy by
his cousin Vitovt, the son of that Keistut who had been strangled by
Iagello. Vitovt, following the example of his predecessors, aimed at
extending the frontiers of Lithuania at the expense of the Russian
territories, and gradually subjugated one after another of them. Vasili
Dmitrievitch was married to the daughter of Vitovt, Sophia;
throughout his reign, he had to keep up friendly relations with his
kinsman, and yet be on his guard against the ambitious designs of
his father-in-law. The Muscovite prince acted with great caution and
prudence, giving way to his father-in-law as far as possible, but
safeguarded himself and Russia from him. He did not hinder Vitovt
from taking Smolensk, chiefly because the last prince of Smolensk,
Iuri, was a villain in the full sense of the word, and the inhabitants
themselves preferred to submit to Vitovt, rather than to their own
prince. When however Vitovt showed too plainly his intentions of
capturing Pskov and Novgorod, the grand prince of Moscow openly
took up arms against his father-in-law and a war seemed imminent;
but in 1407 the matter was settled between them, and a peace was
concluded by which the river Ougra was made a boundary between
the Muscovite and the Lithuanian possessions.

VASILI VASILIEVITCH (AFTERWARDS CALLED “THE BLIND”

OR “THE DARK”)

Vasili Dmitrievitch died in 1425. His

[1425-1435 a.d.] successor, Vasili Vasilievitch, was a man of
limited gifts and of weak mind and will, but
capable of every villainy and treachery. The members of the princely
house had been held in utter subjection under Vasili Dmitrievitch, but
at his death they raised their heads, and Iuri, the uncle of Vasili
Vasilievitch, endeavoured to obtain the grand principality from the
horde. But the artful and wily boyar, Ivan Dmitrievitch Vsevolozhsky,
succeeded in 1432 in setting aside Iuri and assuring the grand
principality to Vasili Vasilievitch. When Iuri pleaded his right of
seniority as uncle, and in support of his claim cited precedents by
which uncles had been preferred, as seniors in years and birth, to
their nephews, Vsevolozhsky represented to the khan that Vasili had
already received the principality by will of the khan and that this will
should be held above all laws and customs. This appeal to the
absolute will of the khan pleased the latter and Vasili Vasilievitch
remained grand prince. Some years later this same boyar, angered
at Vasili because the latter had first promised to marry his daughter
and then married Marie Iaroslavna, the granddaughter of Vladimir
Andreevitch Serpukhovski, himself incited Iuri to wrest the
principality from his nephew. Thus Russia again became the prey of
civil wars, which were signalised by hideous crimes. Iuri, who had
taken possession of Moscow, was again expelled and soon after
died. The son of Iuri, Vasili Kossoi (the Squinting) concluded peace
with Vasili, and then, having treacherously violated the treaty,
attacked Vasili, but he was vanquished, captured, and blinded
(1435). After a few years the following events took place at the
Golden Horde: the khan Ulu Makhmet was deprived of his throne
and sought the aid of the grand prince of Moscow. The grand prince
not only refused him his aid, but also drove him out of the
boundaries of the territory of Moscow. Ulu Makhmet and his
partisans then established themselves on the banks of the Volga at
Kazan, and there laid the foundations of a Tatar empire that during a
whole century brought desolation on Russia. Ulu Makhmet, as ruler
of Kazan, avenged himself on the Muscovite prince for the past, was
victorious over him in battle, and took him prisoner. Vasili Vasilievitch
only recovered his liberty by paying an enormous ransom. When he
returned to his native land, he was against his will obliged to lay
upon the people heavy taxes and to receive Tatars into his
principality and give them estates. All this awakened dissatisfaction
against him, of which the Galician prince Dmitri Shemiaka, the
brother of Kossoi, hastened to take advantage, and joining himself to
the princes of Tver and Mozhaisk, in 1446 he ordered Vasili to be
treacherously seized at the monastery of Troitsa and blinded.
Shemiaka took possession of the grand principality and kept the
blind Vasili in confinement, but observing an agitation among the
people, he yielded to the request of Jonas, bishop of Riazan, and
gave Vasili his liberty, at the same time making him swear that he
would not seek to regain the grand principality. Vasili did not keep his
oath, and in 1447 the partisans of the blind prince again raised him
to the throne.
It is remarkable that from this period the reign
[1447-1448 a.d.] of Vasili Vasilievitch entirely changed in
character. While he had his eyesight, Vasili was
a most insignificant sovereign, but from the time that he lost his
eyes, his reign becomes distinguished for its firmness, intelligence,
and decision. It is evident that clever and active men must have
ruled in the name of the blind prince. Such were the boyars: the
princes Patrikeev, Riapolovski, Koshkin, Plesktcheev, Morozov, and
the famous voyevods, Striga-Obolenski and Theodore Bassenok, but
above all the metropolitan Jonas.

Jonas Becomes Metropolitan

Jonas was a native of Kostroma. When

he was made bishop of Riazan he did not in
any wise become a partisan of the local
views, his sympathies inclined to Moscow
because, in conformity with the conditions
of that epoch, Jonas saw in Moscow alone
the centre of Russian unification. In 1431, at
the death of the metropolitan Photius,
Jonas was elected metropolitan, but the
patriarch of Constantinople had already
named the Greek Isidore to that office. This
Isidore had participated in the capacity of
Russian metropolitan, in the Florentine
council which had proclaimed the union of
the Greek church with the Roman, the pope
of Rome to be the head of the Universal
church. Isidore, together with the patriarch
of Constantinople and the Byzantine
emperor had submitted to the pope; for
Isidore was at heart a Greek: all his aims
Russian Woman
 were directed to the salvation of his
perishing country, and like many other
Greeks he hoped through the pope to arouse Europe against the
Turks. It was these hopes that had caused the Greeks of that time to
sacrifice the independence of their church. In the eyes of Isidore
Russia too was to serve as an instrument for Greek patriotic designs;
but the union was rejected at Moscow, Isidore was driven out, and
for some years the office of metropolitan of Moscow remained
unoccupied. Kiev had its own metropolitans since the days of Vitovt,
but Moscow did not wish to have anything to do with them. The
bishop of Riazan, Jonas, having been already named metropolitan
by the Russian clergy, enjoyed at Moscow a pre-eminent importance
and influence, and finally, in 1448, this archbishop was raised to the
rank of metropolitan by an assembly of the Russian bishops, without
regard to the patriarch. This event was a decisive breach with the
past, and from that time the eastern-Russian church ceased to
depend upon the patriarch of Constantinople and acquired full
independence. The centre of her supreme power was Moscow, and
this circumstance definitively established that moral importance of
Moscow, which had been aimed for by the metropolitan Peter, which
had been held up by Alexis, and which had received greater
brilliancy from the transfer of the ikon of the Blessed Virgin from
Vladimir. From that time the Russian territories not yet subject to
Moscow and aiming to preserve their independence from her—Tver,
Riazan, Novgorod—were bound to her more closely by spiritual
bonds.
When he had for the third time ascended the throne of Moscow,
the grand prince designated as co-regent with himself his eldest son
Ivan, who was thenceforth called grand prince like his father, as is
shown by the treaties of that period. It was from that time that the
political activity of Ivan commenced and gradually widened; and
there is no doubt that when he attained his majority it was he, and
not his blind father that directed the accomplishment of the events
which led to the strengthening of Moscow. Prince Dmitri Shemiaka,
who had been obliged to promise on his oath to desist from any
further attempts upon the grand principality, did not cease to show
his enmity against Vasili the Dark. The clergy wrote to Shemiaka a
letter of admonishment, but he would not listen to their
remonstrances, and the armies of Moscow marched with the
blessing of Jonas and accompanied by the young prince, against
Shemiaka in Galicia. Shemiaka was defeated and fled to Novgorod,
where the inhabitants gave him a refuge, and Galicia with its
dependencies was again joined to Moscow. Shemiaka continued to
plot against Vasili, took Ustiug, and established himself there; but the
young prince Ivan Vasilievitch drove him out, and Shemiaka again
fled to Novgorod. The metropolitan Jonas issued an edict declaring
Shemiaka excommunicated from the church, forbidding orthodox
persons to eat and drink with him, and reproaching the people of
Novgorod for having received him. It was then decided at Moscow to
put an end to Shemiaka by secretly murdering him; the secretary
Borodati, through Shemiaka’s boyar Ivan Kotov, induced Shemiaka’s
cook to prepare and serve to him a poisoned fowl (1453).
Vasili the Dark died on the 5th of March,
[1462 a.d.] 1462, from an unsuccessful treatment of burns.
He outlived his chief counsellor, the
metropolitan Jonas, by a year, the latter having died on the 31st of
March, 1461.h

A REVIEW OF THE INTERNAL DEVELOPMENT DURING THE

TATAR PERIOD

The beginning of the fourteenth century was the commencement

of a new epoch in the life of Russia; in its two halves two empires
began to crystallize: that of Moscow in the east and that of Lithuania
in the west, and the scattered elements began to gather around the
new centres. Such a centre for eastern Russia was Moscow, until
then an insignificant town, rarely mentioned in the chronicles, being
the share of the younger and therefore less powerful princes. Under
Daniel Aleksandrovitch[22] the town of Moscow constituted the whole
principality. With the acquisition of Pereiaslavl (1302), Mozhaisk
(1303), and Kolomna (1308) this region became somewhat more
extended, but when it fell to the share of Ivan Danilovitch after the
death of his brother Iuri, it was still very insignificant; and yet through
its resources the princes of Moscow managed to become the first in
eastern Russia and little by little to gather round them the whole of
eastern Russia. The rise of the principality of Moscow is one of the
most remarkable phenomena in the history of Russia. It is therefore
not surprising that particular attention should have been directed
towards it by historians, and by the light of their united investigations
the phenomenon becomes sufficiently clear.
In the thirteenth century, under the domination of the Tatars in
eastern Russia, there was a continual struggle amongst the princes
for the title of grand prince, to which they also strove to unite the
possession of Vladimir. We also observe another distinctive feature
of the time, which was that the princes did not remain to live in
Vladimir, but only strove to unite it to their own possessions, and
thus augment them, and, if possible, secure them for their families.
The struggle was for the preponderance of one family over another
through the extension of its territorial possessions. In the Kievan
period, whoever became prince of Kiev, removed to Kiev, and named
someone of his own family as ruler in his own principality, so that if
Kiev were lost and it should pass into another family, he would not
lose his own patrimony.
During the Tatar period we note a new phenomenon: the princes
did not merely separate themselves from their patrimonial lands, but
even from their capitals; for instance: Iaroslav lived in Tver, Basil in
Kostroma, Andrew in Gorodeza, Dmitri in Pereiaslavl, and so on. The
power of a grand prince at that time was only a hegemony, a
preponderance over other princes; as a testimony of their
independence the other princes, the elders of their families (such as
Riazan, Tver, etc.) began also to call themselves grand princes, and
the preponderance of the grand prince of Vladimir little by little lost
its significance. To all this there must yet be added another special
circumstance, that in order for anyone to unite Vladimir and its
territory to his possessions and thus obtain the predominance, a
iarlik or letter of the khan was required; no rights were necessary
and a wide field was open for every guest. Thus there appeared a
new basis for the right of succession: the favour of the khan. To
obtain this favour was the aim of all the princes, to keep it—a
peculiar art. Whoever possessed this art would be the head over all
eastern Russia, and whoever could maintain this position was bound
to subordinate all the rest to himself. In consequence of this, the first
condition for success at that time was a dexterous tactfulness, and
whoever possessed this quality must come out victor. This
dexterousness was a peculiar distinction of the Muscovite princes,
and in it lay the chief cause of their success. They had neither power
nor higher rights, and all their hopes were founded on their own skill
and the favour of the khan. They had no riches, and their patrimonial
lands, poor and secluded, away from the great rivers which were
then the chief means of communication, did not yield them large
means.
But to ensure success with the khan, his wife, and the princes of
the horde, money was necessary; so they became saving and
scraping, and all their capacities were directed to the acquisition of
gain. Their qualities were neither brilliant nor attractive, but in their
position it was only by these sober qualities that anything could be
obtained. Alexander Iaroslavitch (Nevski) pointed out to his
successors that their policy should be to give way when necessary
and to wait when uncertain. He who followed this counsel was
successful; whosoever hurried, like Alexander Mikhailovitch (of
Tver), was a loser in the game.
But while taking advantage of every means of influence at the
horde, the Muscovite princes did not lose sight of those means by
which they could also act within Russia itself. Ivan Danilovitch
managed to induce the metropolitan St. Peter to come to Moscow,
and his successors continued to reside in that town. The alliance
with the spiritual power, the only power that embraced the whole of
Russia, was of extraordinary advantage to the Muscovite princes.
The metropolitan could exert his influence everywhere. Thus
Theognost closed the churches at Pskov when that city offered an
asylum to Alexander Mikhailovitch, and St. Sergius did likewise at
Nijni-Novgorod when it accepted a prince to whom Moscow was
opposed. This alliance was a most natural one: if the princes needed
the authority of the church, the clergy—at that time the
representatives of the most advanced ideas concerning the civil
order—sought to realise that order of which it stood in need even for
its purely economic interests. There is not the slightest doubt that
one of the chief causes of the devotion of the clergy to the views and
policies of the Muscovite princes, lay in its conviction that it was
bound to derive material advantages from the concentration of all
power in the hands of one prince. In fact, while the system of
appanages prevailed, it was, on the one hand, extremely difficult for
the clergy to enjoy its possessions and privileges in security,
because the maintenance of this security depended not on one, but
on many; while on the other hand, the princes of appanages
infringed on clerical privileges more frequently than the grand prince.
The dispersion of the monastic estates over several principalities still
further contributed to the desire of the clergy for the abolition of the
appanage system, which increased the difficulties of managing those
estates. Especially in the case of war among the princes of
appanages, the clergy of one appanage might easily be deprived of
its possessions in another appanage, because at such a time all
means of injuring the enemy were considered permissible.
In the increase of power of the Muscovite princes a leading part
also belongs to the Moscow boyars, whose activity was principally
displayed during the youth or minority of the grand princes.[23]
Such were the principal causes of the strength of the Moscow
princes; to them should be added (according to the historians N. V.
Stankevitch and S. M. Soloviov) the central position of the
principality of Moscow, both in the sense that Moscow is near the
sources of the chief rivers, and that an attack from without must first
fall on the surrounding principalities. But these causes are evidently
secondary and would have no significance without the others:
Moscow is not so far from the other principalities that these
advantages would belong to her alone. It was much more important
that a wise policy, by preserving Moscow from the attacks of the
Tatars, attracted thither an increased population and thus enriched
the principality. A final important cause was the weakening of the
Tatar horde and its dismemberment at the end of this period, of
which the princes of Moscow did not fail to take advantage for their
own ends.b